CN1450405A

CN1450405A - Color imaging method and digital imaging method

Info

Publication number: CN1450405A
Application number: CN03107868.0A
Authority: CN
Inventors: 苔口典之; 星野裕之; 井宏元
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 2002-04-04
Filing date: 2003-04-01
Publication date: 2003-10-22
Also published as: US6696230B2; US20030203324A1; JP2003295404A

Abstract

A color image forming method is disclosed, comprising exposing a silver halide color photographic material and developing the exposed photographic material at 43 to 180 DEG C to form a color image, wherein when the photographic material is exposed so that the light-sensitive layer has a transmission density of a minimum density plus 0.1, the light-sensitive layer comprises dye-clouds having an average diameter of 3.0 to 20.0 mum. There is also disclosed a digital image forming process, wherein image recording information of the photographic material which was formed by use of the color image forming method is converted to digital image information through an image sensor.

Description

Color imaging method and digital imaging method

Invention field

The present invention relates to a kind of color imaging method and the digital imaging method that utilizes it of color silver halide photographic-material.

Background of invention

Silver halide photographic light-sensitive material (below, also be called photographic material simply) as recording materials, it is simple and cost is low and high quality graphic can be provided.These materials have great contribution to the progress of industry and culture, have therefore become indispensable material.

Color silver halide photographic-material such as colour negative carry out colour development to form yellow (Y) after exposure, magenta (M) and cyan (C) dye image form silver-colored image simultaneously, bleach subsequently so that silver-colored image is bleached into silver halide.So the silver halide that forms becomes solvable silver complex and removes from photographic material.Photographic material further carries out stabilization processes to wash any remaining fixer off and to clean photographic material.

The common treatment that is used for colour negative as mentioned above (as, technology C-41 or CNK-4) in, photographic material carries out many treatment steps, usually causes making the processing time problem long relatively and that treating apparatus becomes bigger that becomes.Be problematic in that need water to prepare Treatment Solution and its dissolving work trouble, it is dangerous using relative high pH solution, the useless Treatment Solution of control is a trouble after handling, and the processing of processing effluent is disadvantageous for environmental protection.

Foregoing problems problem in the large scale experiment chamber is less.Recently, site disposal, the facility when so-called microscale experiment chamber constantly increases the color film processing, therefore need compact and photograph system for handling that can obtain rapidly, it in addition can be by layman or part-time staff operation, and simple, safety and to the environment friendliness.In addition, in order further to increase the facility of color film, also need the photograph system for handling is introduced the place of convenience store that photo processing device is not provided as yet and so on, therefore need exploitation a kind of do not discharge effluent with simple and safe mode work and to the compactness of environment friendliness and rapid available photograph system for handling with alternative conventional processing system.Address that need and carry out various trials.For example, JP-A 9-325463 and 10-62938 (below, term, JP-A are not meant to be examined and published Japanese patent application) disclose a technology, and wherein photographic material is placed down on the treatment element and heats this material subsequently to form image in the existence of water.This technology can easily be handled photographic material, is not suitable for this but wherein used photographic material is a kind of certain material and conventional color film that contains color developer.

At present, in this so-called digitizing age, image information uses imageing sensor such as Film scanner to be read to form image by the film optics of taking a picture and handle usually, this image changes into electric signal and digitizing, like this, image information can make use up the copy or hard copy save as signal and carry out Computer Processing to obtain dye image.The digital camera that this imaging process generally is furnished with solid state image sensor and conventional silver salt photographic (as colour negative) by use carries out the image input.But high quality graphic can not be by having low picture element density with narrow dynamic range and compare quite expensive low price digital camera with the film of conventional camera lens coupling and obtain.The integrated availability of photographic silver halide material system is still high.

Address that need and carry out various trials.For example, JP-A 9-325463 and 10-62938 (below, term, JP-A are meant examines the Japanese patent application publication) disclose a technology, and wherein photographic material is placed down on the treatment element and heats this material subsequently to form image in the existence of water.JP-A 11-184055 and 11-65054 disclose a technology, and the developer solution that wherein will comprise color developer applies or is sprayed onto on the photographic material to form dye image.JP-A 2001166449 discloses a kind of use to have washing mechanism and handles the method that is contained in the photographic film in the thrust film cassette along handling the path placement with the developing apparatus to the body net of coating processing solution.The open swelling rate that increases the image receiving material of diffusion transfer photographic material with the coefficient that contrasts phase material 0.2-1.5 of JP-A 1-161236; Handle the photographic material that a kind of adding has developer with JP-A 9-325463 is open by a kind of processing elements of comparing with photographic material with higher water swelling degree.JP-A 2001-350240 discloses a kind of photographic material, comprises the pAg with 4.0-8.5 and comprises that to have length breadth ratio be 5 or bigger and account for the silver halide emulsion liquid layer of the sheet silver halide grain of at least 60% crystal grain projected area; JP-A 2001-350236 discloses a kind of disposal route that is used to obtain high developed silver density; Disclose a kind of disposal route with JP-A 2002-31867, wherein initial the counting of the development of each silver halide grain is 3.0 or more when finishing colour development.The present inventor furthers investigate according to aforementioned content, the result confirms, developed silver forms, the process that dyestuff formed and changed into optical density (OD) can not realize by aforementioned disclosed technology fast processing the time effectively, the common issue with that produces is, these technological processs greatly influence the stability of photographic material, particularly, have the technique change of the photographic material of different maintaining requirements before exposure.

In addition, in the color silver halide photographic-material of above-mentioned processing, valuable resource such as silver are dropped or reclaim its part after handling, like this its utilization factor is still low again.Consider the further exhaustion of limited resources in the future such as silver, need a kind of new method of utilizing resource again.

Summary of the invention

Consider foregoing problems, the present invention is accomplished.Therefore, an object of the present invention is to provide the susceptibility that a kind of use has enhancing, even the adaptability of quick acquisition and the color silver halide photographic-material (being the cheap valuable resource of digital picture) that also has excellent technology stability after long preservation are formed the method for coloured image.

Aforementioned purpose realizes by following content:

1. method that forms coloured image comprises:

To comprise the carrier that has at least one silver halide photosensitive layer that comprises the colour coupler that forms dyestuff on it color silver halide photographic-material imaging exposure and

The photographic material of exposure is carried out colour development with the formation coloured image under 43-180 ℃ development temperature,

Wherein, add 0.1 transmission density if the photographic material exposure makes photosensitive layer have least density, this photosensitive layer comprises the dye cloud that mean diameter is 3.0-20.0 μ m;

2. the color imaging method described in above 1., wherein development temperature is 50 ℃-160 ℃;

3. at the color imaging method described in 1. or 2., the photographic material that wherein carries out colour development has at least 800 ISO speed;

4. at the color imaging method of 1.-3. described in any one, it is 8 or bigger silver halide emulsion crystal grain that wherein at least one photosensitive layer comprises mean aspect ratio;

5. at the color imaging method of 1.-4. described in any one, wherein at least one photosensitive layer comprises the silver halide emulsion crystal grain that average thickness is 0.01-0.07 μ m;

6. at the color imaging method of 1.-5. described in any one, wherein at least a photographic material comprises color developer or color developer precursor;

7. at the color imaging method described in 6., wherein the color developer precursor can discharge p-phenylenediamine (PPD) type color developer;

8. at the color imaging method of 1.-7. described in any one, wherein photographic material comprises picture tone modifier;

9. at the color imaging method of 1.-8. described in any one, wherein photographic material comprises electron transfer agent;

10. at the color imaging method of 1.-9. described in any one, wherein photographic material comprises hydrazine derivate;

11. at the color imaging method of 1.-10. described in any one, wherein photographic material comprises monodispersity and is not less than 0.1% and be lower than 25% organic silver salts;

12. at the color imaging method of 1.-11. described in any one, wherein photographic material comprises Fischer type colour coupler;

13. at the color imaging method of 1.-12. described in any one, wherein photographic material comprises a kind of compound that can form colourless basically compound when with the oxidation product reaction of color developer;

14. a digital imaging method wherein will adopt at the color imaging method of 1.-13. described in any one and the image recording information of the photographic material that forms is converted to digital image information by imageing sensor;

15., wherein will be used to change into digital image information by imageing sensor by the light of photographic material reflection at the digital imaging method described in 14.;

16. the digital imaging method described in 14. or 15. wherein is used to change into digital image information with ruddiness by imageing sensor;

17., wherein change into digital image information and do not remove the processing of silver halide and remove at least a in the processing of the insensitive silver compound of light by imageing sensor at the digital imaging method of 14.-16. described in any one;

18. at the digital imaging method of 14.-17. described in any one, wherein said method is carried out the digital image information conversion by imageing sensor after being included in and finishing colour development, carry out at least a bleaching processing that is selected from, the processing of photographic fixing processing and stabilization processes also comprises that further carrying out digital image information by imageing sensor transforms;

19. utilization of resources method comprises and adopts the color silver halide photographic-material of handling as reclaiming resource.

Detailed Description Of The Invention

Ding Yi ISO speed is according to American National Standard (ANSI) PH2.27 " mensuration of ISO speed that is used for the colour negative of still-picture " and measure in the present invention.Color silver halide photographic-material has different picture quality usually, depend on the colour development condition (as, the chemical composition of used Treatment Solution and pH, temperature, the time, stirring condition, the consumption situation, etc.) and have the ISO speed of different absolute values.In the present invention, photographic material and the processing that is applied to it are considered as one group and in every group ISO speed can be by sensitometry (curve of forming as density D as exposure H and ordinate by horizontal ordinate), determine according to the description of above-mentioned PH2.27.Higher ISO speed causes the effect of the present invention that strengthens, and 250 or bigger ISO speed be preferred and 800 or bigger ISO speed be especially preferred.

One aspect of the present invention is a kind of color imaging method, comprise step: will comprise the color silver halide photographic-material exposure of the carrier that has at least one silver halide photosensitive layer that comprises the colour coupler that forms dyestuff on it and subsequently the photographic material that exposes be carried out colour development under 43-180 ℃ development temperature, if wherein the photosensitive layer exposure makes that having least density adds 0.1 transmission density, this photosensitive layer comprises the dye cloud that mean diameter is 3.0-20.0 μ m, that is, exposed and at least one photosensitive layer of colour development to comprise mean diameter be 3.0-20.0 μ m's, in transmission density is that minimum colour density adds the dye cloud that forms on 0.1 the position.

Dye cloud is known in photographic art, for example is described in United States Patent (USP) 6,505,977 (the 2nd hurdles, 4-7 is capable).Therefore, in general, develop to form dye image with the color silver halide photographic-material exposure and with color developer.Therefore, the silver halide chemical reaction of developer and exposure produces elemental silver crystal grain in each silver halide photosensitive layer of photographic material.Argent forms silver-colored image in this layer.The accessory substance of chemical reaction combines to produce dye cloud to form dye image around each development silver halide grain with the colour coupler of formation dyestuff in being included in this layer.Therefore, dye image is dispersed in the colour coupler around the silver halide grain by the thin oily drop form with about 0.1 μ m and is formed by the coupling reaction of the developer of silver halide oxidation.As a result, obtain the distribution that the thin fluid by the colour coupler dye coloring drips, be called " dye cloud ".

The mean diameter (μ m) of the dye cloud that forms after developing of definition in the present invention can use the high power optical microscope to determine by microscopic examination.Dye cloud is observed from the direction perpendicular to the carrier of the photographic material that develops.The diameter of dye cloud (being expressed as μ m) is defined as the suitable ring diameter of the projected area of dye cloud, that is, area is equivalent to the diameter of ring of the projected area of dye cloud.Observe at least 500 dye cloud and the mean value of observable diameter is defined as mean diameter (μ m).Minimum colour density of the present invention (also being expressed as Dmin) is meant the minimum colour density in the low exposure area in the sensitometry of determining ISO speed.Minimum colour density adds that 0.1 transmission density is meant the density than aforementioned Dmin high 0.1.One of the present invention is characterised in that, the mean diameter that forms the dye cloud of this transmission density in photographic material is not less than 3.0 μ m and is no more than 20.0 μ m.Mean diameter is preferably 6.0-20.0 μ m.The dye cloud that the formation mean diameter surpasses 20 μ m causes blocked up layer, causes serious problem, as the lip-deep crack of film of causing when transporting in photograph and processing procedure.

In color imaging method of the present invention, photographic material developed in the heating down temperature 43-180 ℃ (with preferred 50-160 ℃).Temperature above 180 ℃ surpasses the hot heatproof degree of the photographic material that comprises organic material, causes problem, as the fusing of layer and the bleeding of image.

In colour development, be that least density adds that the amount of the dyestuff that forms on 0.1 the position is preferably 0.001-0.200mmol/m in transmission density ²The amount of formed dyestuff can be determined by the whole bag of tricks.For example, the emulsion layer of the photographic material handled is handled with the protein enzyme and used solvent from gained liquid extraction oil soluble ingredient, after most desirably diluting extraction liquids, formed dyestuff for example utilizes HPLC (high performance liquid chromatography), uses and carry out quantitative measurement according to the pre-determined standard model of amount of dye.Be lower than 0.001mmol/m ²Amount of dye need have the particular dye of the costliness of high absorption coefficient, and surpass 0.200mmol/m ²Amount of dye cause the dyestuff area coverage to descend, wherein formed dyestuff ineffectually changes into transmission density, has problems in the contrast design of high exposure area.

Below describe the color imaging method that relates to photographic silver halide material of the present invention and utilize it in detail.

Silver halide

Being used for silver halide of the present invention can be any halide compositions, comprises silver bromide, iodine silver bromide, silver chloride, chlorine silver bromide, iodine chlorine silver bromide, and silver iodochloride.In general, iodine silver bromide, silver bromide and iodine chlorine silver bromide are preferred for obtaining high-speed, and silver chloride and chlorine silver bromide are preferred for carrying out fast processing.The silver halide emulsion that comprises these silver halide grains can be made according to the method for describing in following document: P.Glafkides, photograph chemistry physics (being published 1967 by Paul MontelCorp.); G.F.Duffin, photograph emulsion chemistry (publishing 1966 by Focal Press); The manufacturing of people's such as V.L.Zelikrnan photograph emulsion and coating (publishing 1964 by FocalPress); JP-A 51-39027,55-142329,58-113928,54-48521,58-4938 and 60-138538; With Japanese science photograph association annual meeting summary.Can adopt acidic precipitation, reaction pattern any and water soluble silver salt and halide salts in neutral precipitation and the ammonia precipitation comprises single splash loading, two splash loadings, and combination, the crystal grain in the presence of excessive silver ion forms (reverse precipitation) and water soluble silver salt and water soluble halogenide is supplied to thin seed crystal with growth crystal grain.

The grain size distribution of silver halide emulsion can be narrow or wide, and emulsion preferably comprises single dispersed crystallites.Single dispersed crystallites as herein described is meant the grain size distribution width, that is, the coefficient of variation of the crystallite dimension that obtains by following formula is no more than 25% and more preferably no more than 20% crystal grain:

(standard deviation/average grain size of crystallite dimension) * 100=grain size distribution width (%)

The average grain size that is used for silver halide grain of the present invention does not specifically limit, and changes into cubical coordinator if crystal particle volume is expressed as, and then edge lengths is preferably 0.01-50 μ m and more preferably 0.01-30 μ m.

The crystal grain form can be almost any, comprise rule format cube, the bicrystal of octahedron or tetrakaidecahedron crystal grain and irregular form is as flaky crystalline grain and its combination.Wherein, flaky crystalline grain is especially preferred.The mean value (mean aspect ratio) that to be used for sheet silver halide grain of the present invention be crystal grain diameter/thickness (length breadth ratio) is 2 or bigger, preferred 3-20 and more preferably those of 4-15.The outside of flaky crystalline grain can be made up of [111] or [100] face basically.Can be in conjunction with [111] and [1001.In the present invention, mean aspect ratio is preferably 8 or bigger.Length breadth ratio is high more, and silver halide grain more closely is filled in the layer, thereby color developer is supplied to the reduction reaction district effectively.Mean aspect ratio has stable defect of insufficient above 20 silver halide grain when it is made.

[111] face preferably accounts at least 50% (more preferably 60-90% and further more preferably 70-95%) of the grain surface of sheet iodine silver bromide or silver bromide crystal grain.The shared ratio of [100] face of Miller exponential representation can be according to T.Tan, J. imaging science, and 29,165 (1985) and obtain, wherein adopt the absorption correlativity of [111] face or [100] face.

It is preferably hexagonal to be used for sheet of the present invention (iodine) silver bromide crystal grain.Sexangle sheet crystal grain is meant those of (111) interarea that has sexangle, and wherein maximal phase adjacent side ratio is 1.0-2.0.The maximal phase adjacent side is than being meant the ratio of hexagonal maximal side degree with minimum edge length.But maximal phase adjacent side ratio is the angle rounding of the sexangle sheet crystal grain of 1.0-2.0, and also can use round sheet crystal grain.The edge lengths of round sheet crystal grain is expressed as when the linetype edge partial linear and prolongs and and the prolongation straight line of the line style part on the adjacent both sides distance between the intersection point when intersecting.At least 1/2 of each limit of sexangle sheet crystal grain preferably is made of with the maximal contiguous edge lengths straight line and is more preferably 1.0-1.5.

Be used for sheet of the present invention (iodine) silver bromide crystal grain and preferably comprise dislocation line.Dislocation line in the silver halide grain can utilize transmission electron microscope at low temperatures, for example, according to the method Direct observation in the following document: J.F.Hamilton, photograph science engineering. 11(1967) 57 and T.Shiozawa, Japanese photograph Science and Technology association magazine, 35(1972) 213.The dislocation line of silver halide grain be preferably placed at from the crystal grain center to outside 0.58L-1.0L and more preferably in the scope of 0.80L-0.98L on the direction of grain surface.Dislocation line points to outside surface by the center and curls usually.Preferably, the silver halide grain of at least 50% number comprises at least one dislocation line.The flaky crystalline grain that contains dislocation line of higher proportion (number) also is preferred.Flaky crystalline grain preferably comprises dislocation line in the marginal portion and in main face in the marginal portion of crystal grain and more preferably.Flaky crystalline grain preferably comprises at least 10 and more preferably at least 20 dislocation lines in the marginal portion.In the present invention, term " comprises dislocation line " and is meant in the marginal portion, dislocation line be present in circumferential section near, near near the angle of or the flaky crystalline grain on limit.Particularly, if (promptly perpendicular to main of the crystal grain center of observing flaky crystalline grain and connecting main face, be regarded as main center of gravity of X-Y scheme) and the lengths table of the line at angle be shown " L ", the marginal portion is meant the zone of corresponding angle outside the figure tie point at distance center 0.50L place of relative particle.

Dislocation line can form by form the origin that misplaces as dislocation line on the precalculated position by known usually method; wherein; introducing on the required position of dislocation line; in forming the process of silver halide grain, with silver salt (as, nitrate) aqueous solution together by two spraying techniques add iodide (as; potassium iodide) aqueous solution; only add iodide solution, add the fine grain that contains iodide or adopt the iodide ion releasing agent, for example be disclosed in JP-A6-11781.Wherein preferably two the injection adds iodide aqueous solution and silver salt solution, adds the crystal grain that contains thin iodide and uses the iodide ion releasing agent.

The iodide ion releasing agent is the compound of a kind of following structural formula (J) expression, and it can discharge iodide ion and be expressed as following structural formula (J) by reacting with alkali or nucleophilic reagent:

Structural formula (J): R-I

Wherein, R is an any monovalent organic radical group.R is preferably alkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclic group, acyl group, carbamyl, alkoxy carbonyl, aryloxycarbonyl, alkyl sulphonyl, aryl sulfonyl, or sulfamoyl.R also is preferably has 30 or lower carbon atom, and more preferably 20 or lower carbon atom and further more preferably 10 or the organic group of lower carbon atom.R can be replaced by at least one substituting group.Substituting group can further be substituted.Substituent preferred example comprises halogen atom, alkyl, aryl, aralkyl, heterocyclic group; acyl group, acyloxy, carbamyl, alkoxy carbonyl, aryloxycarbonyl; alkyl sulphonyl, aryl sulfonyl, or sulfamoyl, alkoxy, aryloxy group; amino, amide group, urea groups, urethane ester group, sulfoamido; sulfinyl, phosphoric acid acylamino-, alkylthio groups, aryl thio group; cyano group, sulfo group, hydroxyl, and nitro.

Iodide ion releasing agent (R-I) is iodo-alkane preferably, iodo-alcohol, iodo-carboxylic acid, iodo-acid amides and its derivant, more preferably iodo-acid amides, pure and mild its derivant of iodo-, further iodo-acid amides and the concrete preferred example that is more preferably replaced by heterocyclic group comprises (iodacetyl amino) benzene sulfonate.

Also can adopt silver chloride except silver bromide and iodine silver bromide, the chlorine silver bromide, silver iodochloride and iodine chlorine silver bromide wherein adopt flaky crystalline grain with [100] main face and the flaky crystalline grain with [111] main face.Sheet silver chloride crystal grain with [100] face is described in United States Patent (USP) 5,314,798, European patent 534,318A and 617,325A, WO 94/22051, European patent 616,255A, United States Patent (USP) 5,356,764,5,320,938 and 5,275,930, JP-A5-204073,5-281640,7-225441 and 6-30116.Mainly the flaky crystalline grain of being made up of [111] face is described in detail in United States Patent (USP) 4,439, and it is that 0.7 μ m or bigger and thickness are 0.07 μ m or lower so-called super-thin sheet-shaped crystal grain that 520. United States Patent (USP)s 5,250,403 disclose the equivalent ring diameter; United States Patent (USP) 4,435,501 disclose one deposits to the lip-deep technology of flaky crystalline grain with making silver salt epitaxy.

In flaky crystalline grain, crystallite dimension is expressed as the diameter that has with the ring of crystal grain projected area area identical, so-called equivalent ring diameter.The crystal grain projected area can be placed on the sample panel and nonoverlapping silver halide crystal particle is calculated by the summation of chip area by electron microscope observation.The average crystal grain diameter of flaky crystalline grain that is expressed as the mean value of crystal grain equivalent ring diameter preferably is not less than 0.30 μ m, more preferably 0.30-5 μ m and further more preferably 0.40-2 μ m.Therefore; Flaky crystalline grain is amplified to 10 by electron microscope, 000-70,000 times of crystal grain projected area of also measuring printing.Average crystal grain diameter (φ) is determined by following formula:

Average crystal grain diameter φ=(∑ n _iφ _i)/n

Wherein n is number of die and the n that measures _iBe that diameter is φ _iThe frequency of crystal grain.In measurement, select at least 1,000 crystal grain at random.

The thickness of silver halide grain can be observed crystal grain from vergence direction by electron microscope and determine.The thickness that relates to flaky crystalline grain of the present invention is preferably 0.01-1.0 μ m, more preferably 0.01-0.1 μ m and best 0.01-0.07 μ m.In addition, relate to sheet silver halide grain of the present invention and preferably have narrow thickness distribution.Therefore, the width that distributes with undefined die thickness preferably is no more than 25% and more preferably no more than 20%:

The width (%) that (standard deviation/average thickness of thickness) * 100=die thickness distributes

Consider length breadth ratio and die thickness, preferably be not less than 20 with undefined plate degree (A):

A＝ECD/b ²

Wherein, ECD is that averaging projection's diameter (μ m) and b are die thickness.Averaging projection's diameter is the quantity mean value of the diameter of the area ring suitable with the crystal grain projected area.

Relate to sheet silver halide grain of the present invention and preferably have narrow iodide content distribution.Therefore, distribute with undefined intercrystalline halide content and preferably be no more than 25% and more preferably no more than 20%:

The width that halide content distributes=(standard deviation of halide content/average halide content) * 100 (%)

Being used for silver halide grain of the present invention and can being having at least two kinds has the core/shell type structure of the layer structure that different basically halogenide form or has equal phase composition at intragranular at intragranular.The average iodide content that relates to silver halide emulsion of the present invention preferably is no more than 20mol% and more preferably 0.1-10mol%.

In the present invention, also can use so-called halogenide transformant crystal grain.The halogenide inversion quantity is preferably the 0.2-2.0mol% based on silver.The time that transforms can be in the physics maturing process or afterwards.The moisture halogenide that is lower than the halogenide composition that transforms on the preceding grain surface by adding and solubility product silver-colored or carefully silver halide grain carries out the halogenide conversion.Compact grained is preferably dimensioned to be and is no more than 0.2 μ m and more preferably 0.02-0.1 μ m.

Silver halide grain can be at nucleation or growth phase and at least a cadmium salt that is selected from, zinc salt, lead salt, thallium salt, iridium salt (comprising complex salts), the metallic ion of rhodium salt (comprising complex salts) and molysite (comprising complex salts) adds together so that these metallic ions are included in the inside or the surface of crystal grain.

During silver halide emulsion of the present invention, is 5 at mean molecular weight in preparation preferably, and 000-70,000 low molecular weight gelatine or methionine content are lower than under the existence of gelatin of 30 μ mol/g and carry out nucleation.At the methionine content of nucleation stage more preferably less than 20 μ mol/g and further more preferably 0.1-10 μ mol/g.The mean molecular weight of low molecular weight gelatine is more preferably 6,000-50,000 and further more preferably 7,000-30,000.Be lower than 30 μ mol/g for methionine content is reduced to, effectively use oxygenant that the gelatin of alkali treatment is carried out oxidation processes.The oxygenant that can be used for the gelatin oxidation processes comprises hydrogen peroxide, ozone, peroxy acid, halogen, thiosulfonic acid compound, quinine and organic peracid.Hydrogen peroxide preferably wherein.

Silver halide emulsion of the present invention can carry out desalination with the removal soluble salt when finishing grain growth, or can not desalination.Desalination can be carried out according to the mode that for example is described in Research Disclosure (below, also be called RD simply) 17643.

In the present invention, can be with at least two kinds of emulsions that prepare separately with any ratio blend.In addition, can use the silver halide that is described in JP-A 2002-55410 0054-0065 joint and JP-A 6-118593 0060-0078 joint.

Sensitization

Light activated silver halide emulsion is those of chemical sensitization.The chemical sensitization method that can be used for silver halide emulsion of the present invention comprises known chalcogen sensitization such as sulphur sensitization usually, selenium sensitization and tellurium sensitization are used gold, the novel metal sensitization of platinum or palladium, reduction sensitization or its combination for example are described in JP-A 3-110555 and 5-241267.

Preferred sulfur sensitizer and the selenium sensitizer of using is as the chalcogen sensitizer that can be applicable to silver halide emulsion of the present invention.The example of sulfur sensitizer comprises thiosulfate, allyl thio acylamino thiourea, and allyl sulfide is for isocyanates, cystine, to the toluene thiosulfonate, rhodanine, and inorganic sulfur (the simple material of sulphur).The addition of sulfur sensitizer depends on the kind or the expected effect of emulsion, is preferably 5 * 10 ^-10-5 * 10 ^-5And more preferably 5 * 10 ^-8-3 * 10 ^-5The mol/mol silver halide.

As golden sensitizer, use various gold complexs and gold chloride and aurosulfo.Ligand compound comprises the dimethyl rhodanine, thiocyanic acid, mercapto-tetrazole and mercapto-triazole; The addition of gold sensitizer depends on the kind of emulsion, the kind and the slaking condition of compound, is preferably 1 * 10 ^-8-1 * 10 ^-4And more preferably 1 * 10 ^-8-1 * 10 ^-5The mol/mol silver halide.

Chemical sensitization can for example, be carried out according to the method that is described in JP-A 62-253159 at nitrogen-containing heterocycle compound.The antifoggant of Miao Shuing can add when finishing chemical sensitization after a while.Particularly, the method that is described in JP-A 5-45833 and 62-40446 can be applicable to this.The pH in chemical sensitization stage is preferably 5.3-10.5 and more preferably 5.5-8.5; PAg is preferably 6.0-10.5 and more preferably 6.8-9.0.

The coating weight that is used for silver halide of the present invention is 1-10g/m ²(being expressed as the equivalent that changes into silver).

When preparation related to silver halide of the present invention, the reduction sensitization can be used in combination with aforementioned chemical sensitization.By silver halide emulsion being remained in the best reducing atmosphere, provide reduction sensitization nuclear on the inside or the surface of silver halide grain.The reduction sensitization is preferably carried out in the process of growth silver halide grain.A kind of method that is used to carry out sensitization in the grain growth process is not only used growth crystal grain and is reduced, and interrupts the grain growth and the sensitization of reducing, the crystal grain of the reduction-sensitization of growing subsequently.Particularly, reductive agent and/or water soluble silver salt are added silver halide emulsion.

The preferred example of reductive agent comprises the thiourea dioxide, ascorbic acid and its derivant.In addition, preferred reductive agent comprises polyamine such as hydrazine and Diethylenetriamine, dimethyamine borane, and sulphite.The addition of reductive agent is transformable, depends on the kind of reductive agent, crystallite dimension, the temperature of the composition of silver halide grain and crystalline nature and environmental baseline such as reaction system, pH and pAg.For example, the thiourea dioxide of 0.01-2mg/mol silver halide is preferred; With the ascorbic acid of 0.2-50g/mol silver halide be preferred.The reduction sensitization is 40-80 ℃ in temperature preferably, and pH is that 5-11 and pAg carried out in 10-200 minute under the 1-10.Silver nitrate is preferably used as the water soluble silver salt.So-called silver-colored slaking is undertaken by adding the water soluble silver salt as a kind of mode that is used to reduce sensitization.PAg in silver-colored maturing process is preferably 1-6 and more preferably 2-4.Temperature, time and pH are in above-mentioned scope.

The effect of the reductive agent that adds in expeced time in the crystal grain forming process can be by adding oxygenant such as hydrogen peroxide or its addition product, peracid salt, ozone, I ₂And thiophene is to hinder or to stop to reduce sensitization and passivation.Oxygenant can be formed up to the golden sensitizer of adding (or chemical sensitizer) any time adding before from the beginning silver halide grain.

Have spectrum sensitivity (or colored susceptibility) in order to be used in light activated silver halide of the present invention, as green sensitive degree and red sensitive degree, light activated silver halide emulsion methine type dye or other dyestuff spectral sensitization.Blue responsive emulsion can be carried out spectral sensitization in blue region.Available dyestuff comprises, for example, cyanine dyes, merocyanine dyes cooperates cyanine dyes, auxiliary section cyanine dye, full polarity cyanine dyes, hemicyanine dye, styryl dye and half oxonol dye.Particularly, dyestuff for example is disclosed in United States Patent (USP) 4,617,257; JP-A59-180550,64-13546,5-45828, and 5-45834.Can separately or be used in combination these dyestuffs.The combination of sensitizing dyestuff is generally used for hypersensization or regulates the spectrum sensitivity wavelength.The compound (so-called super sensitizer) that self does not have the dyestuff of spectrum-sensibilization or do not absorb visible light and have a hypersensization can be included in the emulsion (for example be described in United States Patent (USP) 3,615,641 and JP-A 63-23145) with sensitizing dyestuff.These super sensitizers can be in chemical ripening process, or before or after, or before or after the silver halide grain nucleation, add, for example be described in United States Patent (USP) 4,183,756 and 4,225,666.These sensitizing dyestufves and super sensitizer can be by in organic solvent such as methyl alcohol solution or add with the form of dispersion in gelatin or surfactant solution.Addition is 1 * 10 ^-8-1 * 10 ^-2The mol/mol silver halide.

Adjuvant

The hydrophilic protecting colloid that is used to prepare photographic silver halide material of the present invention not only comprises the gelatin that is used for conventional silver halide emulsion; and comprise gelatin (phthalated gelatin) and synthetic or the natural hydrophilic polymer such as the water-soluble cellulose derivative of gelatine derivative such as acetyl group gelatin and phthalic ester.

In photographic silver halide material of the present invention, adopt various techniques known in the art and adjuvant.Except light activated silver halide emulsion liquid layer, for example provide auxiliary layer such as protective seam, light filter layer, anti-halation layer; cross light incised layer and backing layer, comprising chemical sensitizer, novel sensitizer; sensitizing dyestuff, super sensitizer, colour coupler; high boiling solvent, antifoggant, stabilizing agent; development restrainer, bleaching accelerator, anti-coloring agent; the formalin scavenger, picture tone modifier, rigidizer; surfactant, thickening agent, plastifier; lubricant, UV absorbing agent, anti-irradiation dyestuff; the light filter light absorbing dyestuff, germifuge, polymer emulsion; heavy metal, antistatic agent, and matting agent.These adjuvants are described in detail in RD 176, project/17643 (Dec, 1978); Ibid 184, and project/18431 (August, 1979), ibid 187, project/18716 (November, 1979); With ibid 308, project/308119 (Dec, 1989).

Below provide the specific compound that is described in aforementioned RD.

Adjuvant	??????????RD-17643		???RD-18716	??????????RD-308119
	??????????RD-17643		???RD-18716	??????????RD-308119		Page or leaf	Chapters and sections	Page or leaf	Page or leaf	Chapters and sections
	Chemical sensitizer	????23	????III	648 is upper right	????996	Page or leaf	Chapters and sections	Page or leaf	Page or leaf	Chapters and sections	?????III
Sensitizing dyestuff	Chemical sensitizer	????23	????III	648 is upper right	????996	????23	????IV	????648-649	????996-998	?????IV	?????III
Sensitizing dyestuff	The desensibilization dyestuff	????23	????IV	???????-	????998	????23	????IV	????648-649	????996-998	?????IV	?????IV
Dyestuff	The desensibilization dyestuff	????23	????IV	???????-	????998	????25-26	????VIII	????649-650	????1003	?????VIII	?????IV
Dyestuff	Development accelerant	????29	????XXI	648 is upper right	????-	????25-26	????VIII	????649-650	????1003	?????VIII	??????-
The antifoggant stabilizing agent	Development accelerant	????29	????XXI	648 is upper right	????-	????24	????IV	648 is upper right	????1006-1007	?????VI	??????-
The antifoggant stabilizing agent	Whitening agent	????24	????V	??????-	????998	????24	????IV	648 is upper right	????1006-1007	?????VI	?????V
Rigidizer	Whitening agent	????24	????V	??????-	????998	????26	????X	651 left sides	????1004-1005	?????X	?????V
Rigidizer	Surfactant	????26-27	????XI	650 right sides	????1005-1006	????26	????X	651 left sides	????1004-1005	?????X	?????XI
Antistatic agent	Surfactant	????26-27	????XI	650 right sides	????1005-1006	????27	????XII	650 right sides	????1006-1007	?????XIII	?????XI
Antistatic agent	Plastifier	????27	????XII	650 right sides	????1006	????27	????XII	650 right sides	????1006-1007	?????XIII	?????XII
Lubricant	Plastifier	????27	????XII	650 right sides	????1006	????27	????XII	?????-	?????-	??????-	?????XII
Lubricant	Matting agent	????28	????XVI	650 right sides	????1008-1009	????27	????XII	?????-	?????-	??????-	?????XVI
Cementing agent	Matting agent	????28	????XVI	650 right sides	????1008-1009	????26	????XXII	??????-	????1003-1004	?????IX	?????XVI
Cementing agent	Carrier	????28	????XVII	??????-	????1009	????26	????XXII	??????-	????1003-1004	?????IX	?????XVII

Color developer

In the present invention, can use a kind of when the reduction of silver halide or organic silver salts oxidized and form oxidation product, and can with the colour coupler coupling time, form the color developer of dyestuff, or can form the precursor (being also referred to as color developer precursor or enclosed type color developer) of the color developer of color developer when alkali or nucleophilic reagent through being heated.

The example of color developer and color developer precursor comprises that compound (C-1) to (C-16), is described in JP-A 4-86741, the 7-9 page or leaf; With water-soluble color developer and its hydrochloride, sulfate or tosilate (1)-(26) are described in JP-A 3-246543, the 6-10 page or leaf.Other example comprises sulfonamido phenol type developer, is described in JP-A 9-15806; Hydrazine type developer is described in JP-A5-241282,8-234388,8-286340,9-152700,9-152701,9-152702,9-152803 and 9-152704; Hydrazone type developer is described in JP-A 7-202002 and 8-234390; Be described in JP-A 2002-55418, the developer of 0103-0108 joint.

In the present invention, preferably use the color developer precursor to increase the storage stability of color developer.Its example comprises indoaniline type compound, is described in United States Patent (USP) 3,342,597; The schiff's base type compound is described in United States Patent (USP) 3,342,599, RD 14,850 and ibid 15,159; The aldol compound is described in RD 13,924; Metal complex salts is described in United States Patent (USP) 3,719,492; With urethanes type compound, be described in JP-A 53-135628.In addition, the color developer precursor that is expressed as structural formula (1)-(6) release p-phenylenediamine (PPD) that is described in JP-A 2002-55418 also is preferred, and particularly, the compound that is expressed as structural formula (2) has excellent storage stability and colour development ability.Also can use to be described in WO 01/96,954 WO01/96,954, European patent 1,164,417,1,164,418,1,158,358,1,158,359,1,160,612,1,113,316 and 1,113,325; United States Patent (USP) 6,319,640,6,306,551,6,312,879,2001/12886; The compound of JP-B 8-3614 and 8-3616 (below, term, JP-B are called the Jap.P. publication).

The example of color developer and colour coupler comprises and is described in United States Patent (USP) 3,531, the combination of 256 p-phenylenediamine (PPD) type developer and phenol or active methylene group colour coupler and be described in United States Patent (USP) 3,761,270 the para-aminophenol developer and the combination of active methylene group colour coupler.Being combined in of sulfonamido phenol and four-equivalent colour coupler has excellent raw material stability when being included in the photographic material, for example be described in United States Patent (USP) 4,021, and 240 and JP-A 60-128438.

These color developers and its precursor can be included in photographic material or the treatment element (handle sheet material or be also referred to as the medium that the available compound of taking a picture is provided), or are included in the solution that will be provided on the photographic material.In the present invention, color developer or its precursor are included in the photographic material.Be included in and design system in the photographic material with excellent adaptive capacity to environment and quick availability.If be included in the photographic material, even after storing, also can obtain higher stability.In this case, preferably use a kind of compound that reduces silver salt necessarily.

If add photographic material or treatment element, the addition of color developer or its precursor is preferably 0.05-10mmol, more preferably 0.1-5mmol and further more preferably 0.2-2.5mmol/m ²Photosensitive layer.

Picture tone modifier

Relate to photographic material of the present invention and preferably comprise picture tone modifier.Particularly, picture tone modifier and organic silver salts or reductive agent are existed simultaneously, strengthen the effective transmission of silver ion like this.Is used for preferred picture tone modifier of the present invention and is described in RD 17029, and object lesson comprises following:

Acid imide (for example, phthalimide), cyclic imide, pyrazolin-5-one, and quinazolinone (for example, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenyl urazole, quinazoline and 2,4-thiazoline diketone); Naphthalimide (for example, N-hydroxyl-1,8-naphthalimide); Cobalt complex (for example, hexamine trifluoroacetic acid cobalt), mercaptan (for example, 3-sulfydryl-1,2,4-triazole); N-(aminomethyl) aryl dicarboxyl acid imide [for example, N-(dimethylaminomethyl) phthalimide]; Pyrazoles is obstructed, the combination of isothiuronium salts derivant and some kind optical white (for example, N, N '-hexa-methylene (1-carbamyl-3, the 5-dimethyl pyrazole), 1,8-(3,6-two oxa-octanes) two-(trifluoroacetic acid isothiourea), and the combination of 2-(trisbromomethyl-sulfonyl) benzothiazole); Merocyanine dyes (for example, 3-ethyl-5-((the inferior thiazolinyl of 3-ethyl-2-benzo-(the inferior thiazolinyl of benzo))-1-methyl ethylidene-2-sulfo--2,4-oxazolidinedione); Phthalazone, phthalazinone derivatives or its slaine (for example, 4-(1-naphthyl) phthalazone, 6-chlorine phthalazone, 5,7-dimethyl phthalazone and 2,3-dihydro-1,4-phthalazine diketone); The combination of phthalazone and sulfinate derivant (for example, 6-chlorine phthalazone and benzene sulfinic acid sodium salt, or 8-methyl phthalazone and to sodium trisulfonate); The combination of phthalazines and phthalic acid; Phthalazines (comprising the phthalazines addition compound product) and at least a maleic anhydride that is selected from, and phthalic acid, 2,3-naphthalene dicarboxylic acids or adjacent phenylene acid (o-phenylenicacid) derivant and its acid anhydrides are (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid, and tetrachlorophthalic tetrachlorophthalic anhydrid) combination of compounds; Quinazoline diones, benzoxazine ， phenoxazine derivant, benzoxazine-2, the 4-diketone (for example, 1,3-benzoxazine-2,4-diketone); Pyrimidine and asymmetric-triazine (for example, 2, the 4-dihydroxy-pyrimidine) and four azepine pentalene derivants (for example, 3,6-dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-four azepine pentalenes).Preferred image color controlling agent comprises 2,3-phthalazone or phthalazines, and it preferably is used in combination with phthalic acid.Content is preferably 0.05-0.5g and more preferably 0.1-0.3g/m ²Photosensitive layer.

Colour coupler

Below be construed to toner.Be used for colour coupler of the present invention and refer to the compound that forms dyestuff in the time of to react at oxidation product with above-mentioned color developer.Be used for preferred couplers of the present invention and comprise having and be expressed as the compound of following structural formula (Cp-1), for example be described in JP-A 2001-154325 to the structure of (Cp-12).Cp-1???? Cp-2????

Cp-3???? Cp-4???? Cp-5???? Cp-6????

Cp-9???????????????????Cp-10

?

Cp-11??????????????????Cp-12? ???

These materials generally are called active methylene group, pyrazolone, Bi Zuo oxazole, phenol and naphthols.

The colour coupler that is expressed as structural formula (Cp-1)-(Cp-4) is called active methylene group type colour coupler.In structural formula (Cp-1)-(Cp-4), R ₂₄Expression respectively can substituted acyl group, cyano group, nitro, aryl, heterocyclic group, alkoxy carbonyl, aryloxycarbonyl, carbamyl, sulfamoyl, alkyl sulphonyl, and aryl sulfonyl; R ₂₅The expression alkyl, R ₂₅Expression respectively can substituted alkyl, aryl or heterocyclic radical.In structural formula (Cp-4), R ₂₆Expression can substituted aryl or heterocyclic radical.R ₂₄, R ₂₅And R ₂₆Substituent example comprise alkyl, naphthenic base, alkenyl, alkynyl, aryl, heterocyclic group, alkoxy; aryloxy group, cyano group, halogen atom, amide group, sulfonamido, carbamyl, sulfamoyl; alkoxy carbonyl, aryloxycarbonyl, alkyl amino, arylamino, hydroxyl, sulfo group etc.R ₂₄Be preferably acyl group, cyano group, carbamyl, or alkoxy carbonyl.

In structural formula (Cp-1)-(Cp-4), the group that Y leaves away when representing hydrogen atom or can carry out coupling reaction at the oxidation product with color developer.As the negative ion of two-equivalent colour coupler uncouple the example of group of symbasis group comprise halogen atom (as, chlorine, bromine); alkoxy (as, methoxyl, ethoxy); aryloxy group (as; phenoxy group, 4-cyano-benzene oxygen, 4-alkoxycarbonylphenyl); alkylthio groups (as; the methyl sulfo-, ethylenebis dithiocarbamate, butyl sulfo-); the aryl thio group (as; the phenyl sulfo-, the tolyl sulfo-), alkyl-carbamoyl (as; the methylamino formoxyl; formyl-dimethylamino, ethylamino formoxyl, dibutylamino formoxyl; formyl-dimethylamino; formyl-dimethylamino, piperidyl amino formoxyl, morpholino carbamyl); aryl-amino-carbonyl (as; the phenyl amino formoxyl, aminomethyl phenyl carbamyl, ethylphenyl carbamyl; the benzyl phenyl carbamyl); alkylsulfamoyl group (as, methyl sulfamoyl, dimethylamino sulfonyl; the ethyl sulfonamide; the diethyl amino sulfonyl, dibutylamine sulfonyl, piperidyl sulfamoyl; the morpholino sulfamoyl); ammonia aryl sulfonyl (as, phenyl sulfamoyl base, aminomethyl phenyl sulfamoyl; the ethylphenyl sulfamoyl; the benzyl phenyl sulfamoyl), cyano group, alkyl sulphonyl (as; methane sulfonyl; the ethane sulfonyl), aryl sulfonyl (as, the phenyl sulfinyl; 4-chlorphenyl sulfonyl p-toluenesulfonyl); alkyl carbonyl oxy (as, acetoxyl group, propionyloxy; butyryl acyloxy); aryl-carbonyl oxygen (as, benzoyl, toluyl oxygen base; anisyl oxygen base (anicyloxy)); with the nitrogen heterocyclic ring group (as, imidazole radicals, benzotriazole base).

Comprise hydrogen atom as the uncouple example of group of symbasis group of the negative ion of four-equivalent colour coupler, formoxyl, carbamyl, the methylene of replacement (as, substituting group; Aryl, sulfamoyl, carbamyl, alkoxy, imino group and hydroxyl), acyl group, and sulfonyl.In structural formula (Cp-1)-(Cp-4), R ₂₄And R ₂₅, or R ₂₄And R ₂₆Can mutually combine to form ring.

Structural formula (Cp-5) expression so-called 5-pyrazolone (5-pyrazoloe) type magenta colour coupler, wherein R ₂₇The expression alkyl, aryl, acyl group, or carbamyl; P ₂₈Expression has the phenyl of at least a halogen atom, alkyl, cyano group, alkoxy, alkoxy carbonyl, or amide group; Y is identical with the definition in the structural formula (Cp-1)-(Cp-4).

In being expressed as the 5-pyrazolone type magenta colour coupler of structural formula (Cp-5), preferred a kind of R with aryl or acyl group ₂₇R with the phenyl that is replaced by at least one halogen atom ₂₈Therefore, R ₂₇Be aryl such as phenyl, 2-chlorphenyl, 2-methoxyphenyl; 2-chloro-5-four decane amido phenyls, 2-chloro-5-octadecyl sulfone amido phenyl and 2-chloro-5-[2-(4-hydroxyl-3-tert-butyl phenoxy group) four decane acylamino-s] phenyl; or acyl group such as acetyl group, valeryl, myristoyl base; 2-[2; 4-two-uncle-amyl group phenoxy group] acetyl group, 2-(2,4-two-uncle-amyl group phenoxy group) bytyry; benzoyl and 3-(2,4-two-uncle-amyl group phenoxy group acetylamino) benzoyl.These groups can be substituted.Substituent example comprises and comprises carbon atom, oxygen atom, the organic substituent of nitrogen-atoms or sulphur atom and halogen atom.R ₂₈The phenyl that is preferably replacement is as 2,4,6-trichlorophenyl, 2,5-dichlorophenyl or 2-chlorphenyl.

Structural formula (Cp-6) expression pyrazolo pyrroles (pyrazoloazole) type colour coupler, wherein R ₂₉Expression hydrogen atom or substituting group; Z represents to be substituted the atomic radical that needs that base (comprising condensed ring) replaces form the pyrrole ring that contains 2-4 nitrogen-atoms; Y is identical with the definition in the aforementioned structural formula (Cp-1)-(Cp-4).

In being expressed as the pyrazolo pyrroles type colour coupler of structural formula (Cp-6), be described in United States Patent (USP) 4,500,630 imodizo[1,2-b] pyrazoles, be described in United States Patent (USP) 4,540,654 pyrazoles [1,5-b]-1,2,4-triazole and be described in United States Patent (USP) 3,725,067 pyrazoles [5,1-c]-1,2, the 4-triazole is being preferred aspect the absorption characteristic of formed dyestuff; And pyrazoles [1,5-b] 1,2, the 4-triazole is preferred aspect photostability.Be used for substituent R ₂₉Substituting group and the pyrrole ring that is expressed as Y or Z for example be described in detail in United States Patent (USP) 4,540,654, hurdle 2 the 41st walks to hurdle 8 the 27th row.Particularly, the wherein branched-alkyl that for example is described in JP-A 61-65245 is directly connected to the 2-of pyrazolo pyrrole group, the pyrazolo pyrroles colour coupler on 3 or 6; Be described in the pyrazolo pyrroles colour coupler that in molecule, comprises the sulfone acylamino-of JP-A 61-65245; Be described in the pyrazolo pyrroles colour coupler that comprises alkoxyl phenyl sulfone acylamino-fixed group of JP-A 61-147254; Be described in the pyrazolo pyrroles colour coupler that on the 6-position, comprises alkoxy or aryloxy group of JP-A 62-209457 and 63-307453; With the pyrazolo pyrroles colour coupler that in molecule, comprises carbon acylamino that is described in JPA 2-201443 be preferred.

Be expressed as structural formula (Cp-7) and compound (Cp-8) and be called phenol type colour coupler and naphthol type colour coupler.At structural formula (Cp-7) with (Cp-8), R ₃₀Expression=NHCOR ₃₂,-SO ₂NR ₃₂R ₃₃,-NHSO ₂R ₃₂,-NHCOR ₃₂,-NHSO ₂NR ₃₂R ₃₃,-NHSO ₂NR ₃₂R ₃₃, R wherein ₃₂And R ₃₃Be respectively hydrogen atom or substituting group; R ₃₁The expression substituting group; L is that integer 0-2 and m are integer 0-4; Y is identical with the definition in the structural formula (Cp-1)-(Cp-4); And R ₃₁-R ₃₃Be and R ₂₄-R ₂₆The identical substituting group of substituting group of middle definition.

The preferred example that is expressed as the phenol type colour coupler of structural formula (Cp-7) comprises 2-alkyl amino-5-alkylphenol type colour coupler, is described in United States Patent (USP) 2,369,929,2,801,171,2,772,162,2,895,826,3,772,002; 2,5-diamides base phenol type colour coupler is described in United States Patent (USP) 2,772, and 162,3,758,308,4,126,396,4,334,011,4,327,173, Deutsches Reichs-Patent 3,329,729, JP-A 59-166956; With 2-phenyl urea groups-5-amide group phenol, be described in United States Patent (USP) 3,446,622,4,333,999,4,451,559 and 4,427,767.The preferred example that is expressed as the naphthol type colour coupler of structural formula (Cp-8) comprises 2-carbamyl-1-naphthols, is described in United States Patent (USP) 2,474,293,4,052,212,4,146,396,4,228,233 and 4,296,200; With 2-carbamyl-5-acylamino--1-naphthols, be described in United States Patent (USP) 4,690,200.

The compound that is expressed as structural formula (Cp-9)-(Cp12) is called pyrrolo-triazole colour coupler.In structural formula, R ₄₂, R ₄₃And R ₄₄Expression hydrogen atom or substituting group; Y is identical with the definition in the structural formula (Cp-1)-(Cp-4).Be expressed as R ₄₂, R ₄₃And R ₄₄Substituting group and aforementioned R ₂₄To R ₂₆In definition identical.The preferred example that is expressed as the pyrrolo-triazole type colour coupler of structural formula (Cp-9)-(Cp-12) comprises and is described in European patent 488,248A1,491,197A1 and 545,300 those, R wherein ₄₂And R ₄₃In at least one be to absorb electron group.

Use in addition and condense cyclic phenol type colour coupler, imidazole type colour coupler, pyrroles's type colour coupler, 3-pyridone type colour coupler, active methylene group type colour coupler, 5,5-annelated heterocycles colour coupler and 5,6-annelated heterocycles colour coupler.The example of fused phenol type colour coupler comprises and is described in United States Patent (USP) 4,327,173,4,564,586 and 4,904, and those of 575; The example of imidazole type colour coupler comprises and is described in United States Patent (USP) 4,818,672 and 5,051, and those of 347; The example of pyrroles's type colour coupler comprises those that are described in JP-A 4-188137 and 4-190347; The example of 3-pyridone type colour coupler comprises those that are described in JP-A 1-315736; The example of active methylene group type colour coupler comprises and is described in United States Patent (USP) 5,104,783 and 5,162, and those of 196; 5, the example of 5-annelated heterocycles colour coupler comprises and is described in United States Patent (USP) 5,164,289 pyrrolo-pyrazoles type colour coupler and be described in the pyrrolo-imidazole type colour coupler of JP-A 4-174429; 5, the example of 6-annelated heterocycles colour coupler comprises and is described in United States Patent (USP) 4,950,585 pyrazolopyrimidine type colour coupler and be described in the pyrrolo-triazine type colour coupler of JP-A 4-204730.

Except aforementioned colour coupler, also can use to be described in Deutsches Reichs-Patent 3,819,051A and 3,823,049; United States Patent (USP) 4,840,883,5,024,930,5,051,347,4,481,268; European patent 304,856A2,329,036,354,549A2,374,781A2,379,110A2,386,930A1; JP-A63-141055,64-32260,64-32261,2-297547,2-44340,2-110555,3-7938,3-160440,3-172839,4-172447,4-179949,4-182645,4-184437,4-188138,4-188139,4-1948474-204532, the colour coupler of 4-204731 and 4-204732.

Generally be called yellow colour former, the compound of magenta colour coupler and cyan coupler can be used for photographic silver halide material of the present invention.These compounds are used for autochromy, respectively at blue region (wavelength 350-500nm), show the spectral absorption maximal value in green area (wavelength 500-600nm) and the red area (wavelength 600-750nm) when the oxidation product with color developer reacts.If use hydrazine type or sulfonamide type developer, the dyestuff that forms during coupling has the absorption maximal value being different from the aforesaid wavelength.Therefore need be chosen to the kind of toner according to the kind of used developer.Photographic material of the present invention need not to be designed in blueness, has the spectral absorption maximal value in green and the red area.Formed dyestuff can have spectral absorption in UV or region of ultra-red, it can combine with the absorption in seeing the zone.

Be used for colour coupler of the present invention and can have the polymkeric substance fixed group.Can use any four-equivalent colour coupler and two-equivalent colour coupler, and preferably suitably use them.For example, preferred four-the equivalent colour coupler that is expressed as structural formula (1)-(3) that is described in JP-A 2001-5155 that uses is used for developer, and the two monovalent colour couplers that are expressed as structural formula (4) and (5) that also preferred use is described in JP-A 2001-5155 are used for developer.

Comprise four-and the object lesson of two-equivalent colour coupler be described in document or patent, as " photomechanical theory " (the 4th edition, T.H.James, Macmiller, 1977) 291-334 page or leaf and 354-361 page or leaf; JP-A58-12353,58-149046,58-149047,59-11114,59-124399,59-174835,59-231539,59-231540,60-2951,60-14242,60-23474,60-66249,8-1106088-146552,8-146578 and 9-204031.

Photographic material of the present invention can comprise following sense colour coupler.The colour coupler of revising the non-required absorption of dyestuff comprises and is described in European patent 456, the yellow of 257A1-painted cyan coupler, be described in the yellow-painted magenta colour coupler of aforementioned patent, be described in United States Patent (USP) 4,833,069 magenta-painted cyan coupler is described in the colourless masking coupler agent that is expressed as structural formula (A) (36-45 page or leaf exemplify compound) particularly, of WO 92/11575.The compound (comprising colour coupler) that can form the available compound part of taking a picture by the oxidation product reaction with color developer comprises, for example, development restrainer discharges compound as being described in European patent 378,236A1,11 pages the compound that is expressed as structural formula (I)-(IV), be described in European patent 436,938A2,7 pages the compound that is expressed as structural formula (I) is described in the compound that is expressed as structural formula (1) of JP-A 5-307248, is described in European patent 440,195A2, the 5-6 page or leaf be expressed as structural formula (I), (II) and compound (III) and be described in the compound that is expressed as structural formula (I) of JP-A 6-59411; Part-release compound is as being described in United States Patent (USP) 4,555, the compound that is expressed as LIG-X of 478 claims 1.

Being used for aforementioned colour coupler of the present invention can separately or be used in combination, or is used in combination with other colour coupler.Preferably, colour coupler is included in the layer identical with developer and silver halide emulsion, or in the layer identical with silver halide emulsion.If be included in identical with developer and the silver halide emulsion layer, the amount of colour coupler is preferably 0.05-20mol, more preferably 0.1-10mol and further more preferably 0.2-5mol/mol developer.The amount of comprising of colour coupler is 0.01-1mol and more preferably 0.02-0.6mol/mol silver halide preferably.

Water-repellent additive such as colour coupler and color developer can add the predetermined layer of photographic material according to the method that is described in United States Patent (USP) 2.322,027.In this case, can use to be described in United States Patent (USP) 4,555 470,4,536,466,4,536,467,4,587,206,4,555,476 and 4,599,297; With JP-B 3-62,256 high boiling solvent is that 50-160 ℃ low boiling point solvent combines with boiling point optionally.These colour couplers and high boiling solvent can be used in combination separately.The amount of high boiling solvent preferably is no more than 10g, more preferably no more than 5g and further more preferably 1-0.1g/g water-repellent additive.High boiling solvent also preferably is no more than 1ml, more preferably no more than 0.5ml with further more preferably no more than the 0.3ml/g cementing agent.Also can adopt the process for dispersing that uses polymkeric substance, for example be described in JP-B 51-39,853 and the method for JP-A 51-59943.

In the present invention, photographic silver halide material preferably comprises Fischer and disperses the build colour coupler.For example, the method that is described in JP-A 59-60437 and JP-B 6-64319 can be used for Fischer type colour coupler is dispersed in the alkaline aqueous solution.In this case, will comprise the form adding hydrophilic colloid of the colour coupler of acid groups such as carboxylic acid or sulfonic acid with alkaline aqueous solution.Also carefully the form of the special dispersion of solid adds, and for example is described in JP-A 62-30,242.

If colour coupler is that water is insoluble basically, the fine grain form that this colour coupler can be dispersed in the cementing agent adds.Can use various surfactants that hydrophobic compound is dispersed in the hydrophilic colloid, for example be described in JP-A 59-157636,37-38 page or leaf, table 1.Also can use and be described in JP-A 7-66267 and 7-228589 and Deutsches Reichs-Patent 1,932, the phosphate surfactant of 299A.

Hydrazine derivate

Color silver halide photographic-material of the present invention preferably comprises hydrazine derivate and preferred hydrazine derivate is expressed as following structural formula [H]:

Structural formula [H]

Wherein, A ₀Be respectively can substituted aliphatic group, aromatic group, heterocyclic group, or a G ₀-D ₀Group; B ₀It is end-capping group; A ₁And A ₂All be hydrogen atom, or one of them is that hydrogen atom and another are acyl groups, sulfonyl or oxalyl group, wherein G ₀Be-CO--COCO-,-CS-,-C (=NG ₁D ₁)-,-SO-,-SO ₂-or-P (O) (G ₁D ₁)-group, wherein G ₁Be key, or-O-,-S-or-N (D ₁)-group, wherein D ₁Be hydrogen atom, or aliphatic group, aromatic group or heterocyclic group, prerequisite is if there are a plurality of D ₁, they are identical or different and D mutually ₀Be hydrogen atom, aliphatic group, aromatic group, heterocyclic group, amino, alkoxy, aryloxy group, alkylthio groups or aryl thio group.D ₀Be preferably hydrogen atom, alkyl, alkoxy or amino.

In structural formula (H), the A of structural formula (H) ₀The aliphatic group of representative preferably has 1-30 carbon atom, more preferably has straight chain, branching or the cyclic alkyl of 1-20 carbon atom.Its example is respectively and can be substituted methyl, ethyl, the tert-butyl group, octyl group, cyclohexyl and the benzyl that base (as aryl, alkoxy, aryloxy group, alkylthio, aryl sulfo-, sulfo group-oxygen base, sulfonamido, sulfamoyl, amide group or urea groups) replaces.

The A of structural formula (H) ₀The aromatic group of expression is preferably monocycle or condenses-polycyclic aryl such as phenyl ring or naphthalene nucleus.A ₀The heterocyclic group of expression is preferably and comprises at least one and be selected from nitrogen, and the heteroatomic monocycle of sulphur and oxygen or condense-many rings a kind of comprise pyrrolidine ring, imidazole ring, the tetrahydrofuran ring, morpholine ring, pyridine ring, pyrimidine ring, the quinoline ring, thiazole ring, benzothiazole ring, the residue of thiphene ring or furan nucleus.At A ₀Expression-G ₀-D ₀In the group, G ₀Be-CO--COCO-,-CS-,-C (=NG ₁D ₁)-,-SO-,-SO ₂-or-P (O) (G ₁D ₁)-group and preferred G ₀Be-CO--COCOA-, wherein G ₁Be key, or-O-,-S-or-N (D ₁)-, be D wherein ₁Expression hydrogen atom, or aliphatic group, aromatic group or heterocyclic group, prerequisite is if there are a plurality of D ₀, they can be identical or different mutually.D ₀Be hydrogen atom, aliphatic group, aromatic group, heterocyclic group, amino, alkoxy, aryloxy group, or alkylthio groups, or aryl thio group, and D ₀Be preferably hydrogen atom, alkyl, alkoxy or amino.Aromatic group, heterocyclic group and-G ₀-D ₀Group can be substituted.

Concrete preferred A ₀Be aryl or-G ₀-D ₀Group.A ₀Preferably comprise the group that can not spread or be used to promote to be adsorbed to group on the silver halide.The fixed base that is used as the group that can not spread in fixedly photograph adjuvant such as colour coupler is preferred.Fixed group comprises alkyl, alkenyl, and alkynyl, alkoxy, phenyl, phenoxy group and alkyl phenoxy, they have 8 or more a plurality of carbon atom and be the photograph inertia respectively.The group that is used to promote to be adsorbed on the silver halide comprises, for example, and thiourea group, thioxanthamide group, sulfydryl, sulfide group, thioketones group, heterocyclic group, thio acylamino-heterocyclic group, sulfydryl-heterocyclic group and the absorption that is described in JP-A 64-90439 promote group.

In structural formula (H), B ₀Be end-capping group and preferred-G ₀-D ₀, G wherein ₀Be-CO--COCO-,-CS-,-C (=NG ₁D ₁)-, SO-,-SO ₂-or-P (O) (G ₁D ₁)-group and preferred G ₀Be-CO--COCOA-, wherein G ₁Be key, or-O-,-S-or-N (D ₁)-group, wherein D ₁Expression hydrogen atom, or aliphatic group, aromatic group or heterocyclic group, prerequisite is if there are a plurality of D ₁, they can be identical or different mutually.D ₀Be aliphatic group, aromatic group, heterocyclic group, amino, alkoxy or sulfydryl and preferred, hydrogen atom, or alkyl, alkoxy or amino.A ₁And A ₂All be hydrogen atom, or one of them is that hydrogen atom and another are acyl groups, (acetyl group, trifluoroacetyl group and benzoyl), sulfonyl (methane sulfonyl and tosyl) or oxalyl group (ethoxy oxalyl group).

The object lesson that is expressed as the compound of structural formula [H] comprises the compound H-1 of the paragraph 0046-0051 that is described in JP-A2002-55410 to H-30, but never is limited to these.Other preferred hydrazine derivate comprises, for example, is described in United States Patent (USP) 5,545, and the compound H-1 on 11-hurdle, 505 hurdle 20 is to H-29; Be described in United States Patent (USP) 5,464,738, the compound 1-12 of the 9-11 on hurdle 9.

Can be according to easily synthetic these hydrazine derivates of known usually method.Hydrazine derivate is added photosensitive layer or its adjacent layer that comprises silver halide emulsion.The crystallite dimension and the halogenide that depend on silver halide grain are formed, and the addition of the degree of chemical sensitization and the kind of antifoggant is preferably 1 * 10 ^-6-1 * 10 ^-1Mol and more preferably 1 * 10 ^-5-1 * 10 ^-2The mol/mol silver halide.

Organic silver salts

Color silver halide photographic-material of the present invention preferably comprises known usually organic silver salts to strengthen susceptibility or development capability.

Can be used for the silver salt that organic silver salts of the present invention comprises long-chain fatty acid and contains the carboxylic acid of heterocycle, as ， behenic acid silver, α-(1-phenyltetrazole sulfo-) acetate, for example be described in JP-AN53-49241,49-52626,52-141222,53-36224,53-37626,53-36224 and 53-37610; Silver salt with the compound of imido-for example is described in JP-B44-26582,45-12700,45-18416 and 45-22815; JP-A 52-137321,58-118638, and 58-118639; United States Patent (USP) 4,123,274.Also can use the acetylene silver salt that is described in JP-A61-249044 and be described in the compound that contains sulfydryl of WO 01/96950 and the cooperation salt of silver.Wherein preferably the silver salt of benzotriazole and its derivant (as, benzotriazole silver salt, the silver complex of 5-methylbenzotrazole silver salt) ， behenic acid silver and 1-phenyl-5-sulfydryl-tetrazolium.

Aforementioned organic silver salts can separately or be used in combination, and they prepare in hydrophilic colloid aqueous solution such as aqueous gelatin solution and desalination is used with former state.In addition, formed organic salt being separated also, machinery is milled to fine grained and disperses.

The consumption of organic silver salts is 0.01-10mol and preferred 0.05-3mol, is used in combination with the 1mol photothermographic silver halide.To change into the photosensitive silver salt represented of equivalent of silver and the total amount of organic silver salts is 0.05-30g/m ²And preferred 0.115g/m ²Color silver halide photographic-material of the present invention preferably comprises monodispersity and is not less than 0.1% and be lower than 25% organic silver salts crystal grain.The crystallite dimension of organic silver salts is meant edge lengths, if organic silver salts crystal grain is regular crystal such as cube or octahedra crystal grain.If not regular crystal, crystallite dimension is expressed as the diameter that volume is equivalent to the ball of crystal particle volume, that is, and and the equivalent bulb diameter.Monodispersity (or coefficient of variation of crystallite dimension) is defined as follows:

Monodispersity (%)=(standard deviation of crystallite dimension)/(average grain size) * 100

The preparation monodispersity is lower than 0.1% organic silver salts crystal grain needs great amount of manpower, therefore impracticable.On the contrary, monodispersity surpasses 25% organic silver salts crystal grain and causes irregular image unfriendly.

Antifoggant

Can be used for antifoggant of the present invention and comprise, for example, be described in United States Patent (USP) 3,645,739 higher fatty acid; Be described in the mercury salt of JP-B 47-11113; Be described in the N-halogen compounds of JP-A 51-47419; Be described in United States Patent (USP) 3,700,457, JP-A 51-50725, the sulfydryl of 2-297548 and 2-282241 discharges compound; Be described in the aryl sulfonic acid of JP-A 49-125016; Be described in the lithium carbonate of JP-A 51-47419; Be described in BrP 1,455,271 and the oxygenant of JP-A50-101019; Be described in sulfonic acid and the thiosulfonic acid of JP-A 53-19825; Be described in the sulfo-uracil of JP-A 51-3223; Be described in the sulphur of JP-A 51-26019; Be described in JP-A51-42529, the disulfide of 51-81124 and 55-93149, and polysulfide; Be described in rosin and two terpenes of JP-A51-57435; Be described in the polymeric acid that comprises carboxyl or sulfonic acid group of JP-A 51-104338; Be described in United States Patent (USP) 4,138,265 thiazoline thioketones; Be described in the triazole of JP-A 54-51821 and 55-142331 and United States Patent (USP) 4,137,079; Be described in the thiosulfinate of JP-A55-140883; Be described in JP-A 59-46641, two of 59-57233 and 59-57234-or three-halogenide; Be described in the mercaptan compound of JP-A 59-111636; With the hydroquinone derivative who is described in JP-A 60-198540 and 60-227255.Other preferred antifoggant comprises the antifoggant that contains hydrophilic radical that is described in JP-A 62-78554; Be described in the polymkeric substance antifoggant of JP-A62-121452; With the antifoggant that contains fixed base that is described in JP-A 62-123456.Preferably be described in the colour coupler of the non-formation dyestuff of JP-A1-161239 in addition.In addition, antifoggant such as above-mentioned organic silver salts and the compound that is described in JP-A.

In the present invention, can use various antifoggants and stabilizing agent and its precursor.Its object lesson comprises the compound that is described in aforementioned Research Disclosure, is described in United States Patent (USP) 5,089,378,4,500,627 and 4,614,702, JP-A 64-13564,7-9 page or leaf, the compound of 57-71 page or leaf and 81-97 page or leaf and be described in United States Patent (USP) 4,775,610,4,626,500, with 4,983,494; JP-A62-174747,62-239148,1-150135,2-1105572-1789148, RD17,643 (1978) 24-25 pages or leaves, European patent 1,164,419 and 1,164,421, the compound of JP-A2002-23326 and 2002-31878.

The consumption of these compounds preferably 5 * 10 ^-6-10mol and more preferably 1 * 10 ^-6-5mol/mol silver.

Layer is arranged

In photographic material of the present invention, can on the photosensitive layer or under provide various layer as protective seam, below layer, middle layer, yellow filter layer and anti-halation layer.The backing layer can be provided on the opposite face of carrier.Particularly, can provide a description in the lower floor of United States Patent (USP) 5.051,335; the middle layer that comprises solid pigment is described in JP-A 1-120553, the middle layer that comprises reductive agent or DIR compound of 5-34884 and 2-64634; be described in United States Patent (USP) 5; 017,454 and 5,139; 919; the middle layer that comprises electron transfer agent of JP-A 2-235044 is described in the protective seam that comprises reductive agent of JP-A4-249245 and the combination of aforementioned layers.

Various layers are arranged and be can be applicable to color silver halide photographic-material of the present invention, comprise conventional layer order, and contrary layer order and elementary layer are arranged.

Dyestuff

In color silver halide photographic-material, the dyestuff that will have different absorptions in various wavelength region may is used for anti-halation or anti-irradiation.Because thin collargol particle is used for the yellow filter layer or the anti-halation layer of conventional color silver halide photographic-material, after finishing development, need bleaching process to remove collargol.The photographic material that need not to bleach is desirable for the simplicity that improves this technology.Therefore,, can in technological process, decolour particularly by using dyestuff, leach or shift and finishing dealing with after to the alternative collargol of the less a kind of dyestuff of density contribution.Decolouring or removed dyestuff are meant in technological process, the content of finishing the dyestuff that stays after handling be no more than the dyestuff that before processing, is included in the photographic material 1/3 and preferably be no more than 1/10.Dye component can leach from photographic material in technological process, is transferred to treatment element, or is leuco compound by reactions change in technological process.

These dyestuffs can add silver halide emulsion liquid layer or the insensitive layer of light.In order to make susceptibility and sharpness compatible mutually,, preferably a kind of dyestuff that has absorption in the wavelength region may identical with silver halide emulsion is introduced on the position relative with light source for silver halide emulsion to the particular wavelength region sensitivity.The dyestuff that can be used for photographic material of the present invention comprises known dyestuff usually, as the dyestuff in alkaline soluble or the developer solution or can with the composition of developer solution, as sulfite ion, developer or alkali reaction and the dyestuff that decolours.Its object lesson comprises and is described in European patent 549, the dyestuff of 489A and be described in the exemplary dyes F2 to 6 of JP-A 7-152129.These dyestuffs are used for wherein handling in Treatment Solution the situation of photographic material, the situation of wherein using processing sheet material thermal development photographic material that is preferred for describing after a while.If handle in Treatment Solution, the preferred example that has the dyestuff of absorption in visibility region comprises and is described in JP-A 3-251840,308 pages dyestuff AI-1 to 11.Be described in JP-A 1-280750,2 pages, the hurdle, lower-left be expressed as general formula (I), (II) and infrared absorbing dye compound (III) have better spectral characteristic and do not influence photographic property and owing to residual dye pollutes.The object lesson of preferred compound comprises compound (1)-(45) on the hurdle, 5 pages of lower-lefts, the 3rd page of hurdle to the, lower-left that is described in identical publication.

Dyestuff also can be fixed in the cementing agent with the mordant mordant dyeing by making dyestuff.Can use known mordant of photographic art and dyestuff and its example to comprise and be described in United States Patent (USP) 4,500,626,58-59 hurdle, JP-A 61-88256,32-41 page or leaf, the mordant of 62-244043 and 62-244036.In addition, but use reductive agent and, make the release and be dissolved in Treatment Solution or be transferred to the processing sheet material when developing of the mobilizable dyestuff of alkali, for example be described in United States Patent (USP) 4,559,290 and 4,783,369 by discharging the compound of spread dyestuff with the reductive agent reaction; European patent 220,746A and Kekai Giho 87-6119; Save with JP-A 8-101487 0080-0081.

Also can use the decolouring leuco dye.For example, JP-A 1-150132 has described a kind of prior photographic silver halide material that comprises leuco dye that develops with developer such as organic acid metal salt.Because leuco dye and developer complex decolour by heating or with the base reagent reaction, this combination of leuco dye and developer is preferred for carrying out thermal development.Can use known leuco dye usually, for example be described in 9,84 pages (Kaseihi Kogyekai) of Moriga and Yoshida " Senryo-Yakuhin " volume; " Senrye Binran (dyestuff handbook) " 242 pages (Maruzen, 1970); R.Garner " Advances in Applied Chemistry report " 56,199 (1971); " Senryo-Yakuhin " rolls up 19,230 pages (Kaseihi Kegyekai); " Shikizai " 62,288 (1989); " Senrye Kegye " 32,208.The preferred example of developer comprises sour loam mould developer, phenolics and metal salts of organic acids.

Cementing agent

Be used for photographic material of the present invention or handle the cementing agent of composition layer of material preferably hydrophilic, for example be described in aforementioned RD or JP-A 64-13546, the 71-75 page or leaf.The cementing agent that is used for the silver thermal photographic image forming material is transparent or semitransparent and generally is colourless, comprises natural polymer, synthetic polymer or multipolymer and filming medium.Its illustrative example comprises gelatin, Arabic gum, polyvinyl alcohol (PVA), hydroxyethyl cellulose, cellulose acetate, cellulose acetate-butyrate, polyvinylpyrrolidone/, casein, starch, polyacrylic acid, poly-(methyl methacrylate), poly-(methyl acrylic acid), Polyvinylchloride, polymethylacrylic acid, copolymerization (styrene-anhydrous maleic acid), copolymerization (styrene-acrylonitrile), copolymerization (styrene-butadiene), Pioloform, polyvinyl acetal (as, polyvinyl formal, polyvinyl butyral), polyester, polyurethane, phenoxy resin, polyvinylidene chloride, polyepoxide, polycarbonate, polyvinyl acetate, cellulose esters, and polyamide.To be used for cementing agent of the present invention can be hydrophilic or hydrophobic and transparent hydrophobic cementing agent are used to reduce the atomizing that causes when thermal development, for example, comprises polyvinyl butyral, cellulose acetate, cellulose acetate-butyrate, polyester, polycarbonate, polyacrylic acid, and polyurethane.Wherein preferably polyvinyl butyral, cellulose acetate, cellulose acetate-butyrate and polyester.These cementing agents separately or be used in combination.Coating weight preferably is no more than 100g/m ²With more preferably no more than 20g/m ²

Rigidizer

Photographic material of the present invention or processing material preferably harden with rigidizer.If use hydrophilic adhesive such as gelatin, preferred rigidizer comprises, for example, is described in JP-A59-116655,62-245261,61-18942,61-249054, those of 61-245153 and 4-218044.Its object lesson comprise aldehyde type rigidizer (as; formaldehyde), azacyclopropane (azilidine) type rigidizer, epoxy type rigidizer; vinyl sulfone type rigidizer [as; N, N '-ethylidene-two (vinylsulfonyl acetamido) ethane], N-methylol type rigidizer (as; dimethylolurea); boric acid, metaborate and polymkeric substance rigidizer (as, be described in the compound of JP-A 62-234157).In these rigidizers, vinyl sulfone type rigidizer and chlorotriazine type rigidizer are preferred separately or be used in combination.The consumption of these rigidizers is 0.001-1g and preferred 0.005-0.5g/g hydrophilic adhesive.

Carrier

Be used for carrier of the present invention and be preferably polyolefin such as tygon and polypropylene, polycarbonate, cellulose acetate, polyethylene terephthalate, the plastic film of PEN and Polyvinylchloride, the polystyrene with syndiotactic structure also is preferred.These can be by being described in JP-A 62-117708, the method for 1-46912 and 1-178505 and obtaining.Other carrier that can be used for photographic material of the present invention comprises paper carrier such as asbestos base paper, printing paper, and baryta paper and resin coated paper have the aforementioned plastic film in reflection horizon and are described in the carrier of JP-A62-253195 (29-31 page or leaf).The preferred use is described in 17643,28 pages of aforementioned RD; 18716,647 pages, right hurdle to 648 page, left hurdle; 30710,879 pages carrier.

Carrier described above can be heat-treated being lower than under the temperature of Tg, reduces roller like this and solidifies curling.In addition, carrier can carry out surface treatment to increase the adhesiveness between carrier and the sublayer.Particularly, use glow discharge to handle UV treatment with irradiation, Corona discharge Treatment and flame treatment.

Also adopt and be described in " the carrier of KochigijutSu (known technology) the 5th phase (on March 22nd, 1991 was published by Azutech Co.) 44-149 page or leaf.In addition, have a kind of of Transparent Magnetic Materials on transparent carrier such as PEN dicarboxylate and its.Also can use and be described in RD308119,1009 pages and Product License index volume 92 volumes, 108 pages, the carrier of project " carrier ".If photographic material of the present invention is used for thermal treatment, use therein carrier needs anti-treatment temperature.

Magnetic recording layer

In the present invention, except aforementioned bearer, the carrier with magnetic recording layer can be used for writing down photograph information, for example is described in JP-A 4-124645,5-40321,6-35092 and Japanese patent application 5-58221 and 5-106979.

By on carrier, being coated with the moisture or organic solvent type coating composition that comprises the particles of magnetic material that is dispersed in the cementing agent, provide magnetic recording layer.Be used for particles of magnetic material of the present invention and comprise ferromagnetic iron oxide such as γ-Fe ₂O ₃, Co-applies γ-Fe ₂O ₃, Co-applies magnetic iron ore, contains the magnetic iron ore of Co, ferromagnet chromium dioxide, ferromagnetic metal, ferromagnet alloy, sexangle barium ferrite, strontium ferrite, ferrous acid lead, and calcium ferrite.Wherein, Co-applies ferromagnetic iron oxide such as Co-applies γ-Fe ₂O ₃Be preferred.Can use Any shape such as needle-like, the rice grains, sphere, cube and plane form.Specific surface area preferably is not less than 20m ²/ g and more preferably be not less than 30m ²/ g is in SBET.Saturation magnetization (the σ of ferromagnetic material _s) be preferably 3.0 * 10 ⁴-3.0 * 10 ⁵A/m and more preferably 4.0 * 10 ⁴-2.5 * 10 ⁵A/m.The ferromagnetic material particle can be with alumina or organic material surface treatment.Also available silane coupling agent of ferromagnetic material particle or peptide coupling agent surface treatment for example are described in JP-A 6-161032.Also can use the particles of magnetic material of its surface coverage organic or inorganic material, for example be described in JP-A 4-259911 and 5-81652.

The cementing agent that is used for particles of magnetic material comprises thermoplastic resin, thermoset resin, radiation-hardenable resin, reaction resin, acid-, alkali-or biodegradable polymers, natural polymer (as, cellulose derivative, sugar derivatives) and its potpourri, for example be described in JP-A 4-219569.The Tg of aforementioned resin is 2 for-40 ℃ to 300 ℃ with weight-average molecular weight, 000-1,000,000.Its object lesson comprises the vinyl-type multipolymer, cellulose derivative such as cellulose diacetate, cellulosic triacetate, cellulose-acetate propionate, cellulose acetate-butyrate and three cellulose propionates, acryl resin and polyvinyl acetal resin.Gelatin also is preferred.Wherein, cellulose two (or three) acetic acid esters is especially preferred.Cementing agent epoxy available type, azacyclopropane (azilidine) type, isocyanate-based rigidizer sclerosis.Isocyanate-based rigidizer comprises, for example, and isocyanates such as triclene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, hexylidene diisocyanate, and eylylene diisocyanate; The reaction product of these isocyanates and many alcohol (as, the reaction product of 3mol triclene diisocyanate and 1mol trimethylolpropane) and, for example be described in JP-A 6-59357 by the polyisocyanate that these isocyanates of condensation are made.

With kneader, pin-type grinding machine and ring ball mill are separately or in conjunction with being used for aforementioned magnetic material is dispersed in cementing agent.Can use and be described in JP-A 5-088283 or spreading agent known in the art.The thickness of magnetic recording layer is 0.1-10 μ m, preferably 0.2-5 μ m and more preferably 0.3-3 μ m.The weight ratio of particles of magnetic material and cementing agent is preferably 0.5: 100-60: 100 and more preferably 1: 100-30: 100.The coating weight of particles of magnetic material is 0.005-3g/m ², preferred 0.01-2g/m ²And more preferably 0.02-0.5g/m ²The transmission yellow density of magnetic recording layer is preferably 0.01-0.50, more preferably 0.03-0.20 and further more preferably 0.04-0.15.Magnetic recording layer utilization coating or printing all or with the form of bar provide at the back side of carrier.Magnetic recording layer can pass through air doctor blade, blade, and air knife, extruding is flooded, reverse rollers, transferring roller, intaglio printing, kissing, casting, spraying, dipping, rod applies with extruding.The coating solution that is described in JP-A 5-341436 also is preferred.

Magnetic recording layer can further have various function additives to strengthen lubricated crooked adjusting, antistatic agent, anti-acidblocking agent and a detersive.Can provide functional layer to realize aforementioned functional separately.

Mohs hardness is at least 5 non-spherical inorganic particle and preferably is used as abrasive material in magnetic recording layer of the present invention.Non-spherical inorganic particle is by oxide such as aluminium oxide, chromium oxide, silicon dioxide and titania; Carbonide such as silit and titanium carbide; Or the fine powder adamas is formed.Abrasive material can be with silane coupling agent or peptide coupling agent surface treatment.Particle can add magnetic recording layer or the external coating on magnetic recording layer (as protective seam or lubricant layer).The cementing agent that available cementing agent comprises aforementioned cementing agent and is used for magnetic recording layer is preferred.Photographic material with magnetic recording layer is described in United States Patent (USP) 5,336, and 589,5,250,404,5,229,259,5,215,874; With European patent 466,130.

Below describe the polyester support of the aforementioned photographic material be used to have magnetic recording layer and comprise photographic material, handle, the details of box and its example is described in Kokai-Giho 94-6023 (March15,1994, Hatsumei Kyokai).The polyester that can be used as carrier is made up of as solvent two pure and mild aromatic dicarboxylic acids.The example of aromatic dicarboxylic acid comprises 2,6-, and 1,5-, 1,4-, or 2,7-naphthalene dicarboxylic acids, terephthalic acid (TPA), m-phthalic acid and phthalic acid; Comprise diglycol with the example of glycol, triethylene glycol, cyclohexanedimethanol, bisphenol-A, and bis-phenol.The example of polymkeric substance comprises homopolymer such as polyethylene terephthalate, PEN and poly-cyclohexane-dimethanol terephthalate.Comprise 50-100mol%2, the polyester of 6-dicarboxylic acid is preferred and gathers 2 that the 6-(ethylene naphthalate) is especially preferred.Mean molecular weight is 5,000-200,000.The Tg of polyester is 50 ℃ or higher and preferred 90 ℃ or higher.

Preferably be higher than 40 ℃ and be lower than the temperature of Tg, more preferably be higher than Tg and deduct 20 ℃ and be lower than under the temperature of Tg polyester support heat-treated and solidify curling to reduce roller.Thermal treatment can be carried out under the steady temperature in falling into aforementioned range.In addition, thermal treatment is undertaken by cooling.Heat treatment time is 0.1-1500 hour and preferred 0.5-200 hour.The thermal treatment of carrier can roll form or is undertaken by transmission nethike embrane (web).Surface modification can be by the roughening carrier the surface (as, by being coated with thin conductive inorganic particles such as SnO ₂Or SbO ₂) and realize.Preferably terminad partly provides embossing to increase end portion, prevents otch moving in roller nuclear part like this.These thermal treatments can be carried out in any stage, that is, after the system film of carrier, after thermal treatment, the coating backing layer (as, antistatic agent, lubricant) after the coating antistatic agent, carry out afterwards or after bottom coating and preferably.The UV absorbing agent can be mediated in polyester.Preferred commercially available dyestuff or the pigment that is used for polyester that adds, as Diaresin (derive from Mitsubishi Kasei Co., Ltd.) and Kayaset (derive from Nippcn Kayaku Co., Ltd.) in case optical pumping.

In the present invention, processing can be carried out according to C41 standard method (by Eastman Kodak Co. exploitation) or technology similarly, comprises colour development, bleaching, and photographic fixing and stabilization, Treatment with activating agent also are feasible.In this case, preferably, photographic material has any characteristic in the kinds of processes of being applicable to.

In the present invention, Treatment with activating agent is meant that color developer or its precursor are included in photographic material and/or handle in the material and handle and be to use a kind of solution that does not comprise color developer to carry out.Therefore, Treatment Solution does not contain color developer, and the latter is included in the conventional colour development solution, and alkali or auxiliary developer can comprise wherein like this.Treatment with activating agent for example is described in the prior art document, for example, and European patent 545,491A1 and 565,165A1.The pH of Treatment with activating agent solution is preferably 9 or higher and more preferably 10 or higher.

Auxiliary developer

If photographic material of the present invention is carried out Treatment with activating agent, then use auxiliary developer.Auxiliary developer is meant and can promotes electronics to be transferred to the material of silver halide by color developer in the technology of development silver halide.Auxiliary developer can add auxiliary process solution or be included in the photographic material.The development that use comprises the alkaline aqueous solution of auxiliary developer is described in RD N17643, the 28-29 page or leaf; 18716,651 pages of RD, left hurdle to right hurdle; With RD 30710, the 880-881 page or leaf.Be used for the compound that auxiliary developer of the present invention preferably meets the release electronics of Kendall-Perz rule, as be described in JP-A 2002-23296,0118-0123 joint be expressed as general formula (ETA-I) and (ETA-II) those.Wherein, the compound that is expressed as structural formula (ETA-I) is especially preferred.Formula (ETA-1)

Formula (ETA-2)

In following formula, R ₅₁And R ₅₂Be hydrogen atom, alkyl, naphthenic base, alkenyl, aryl or heterocyclic group.

If auxiliary developer is included in the photographic material, then auxiliary developer can precursor forms be included to increase the storage stability of photographic material.

The example of the precursor of developer comprises that the compound (ETP-1) that is described in JP-A 2000-89425 is to (ETP-97).These compounds may be dissolved in water or solvent such as ethanol, and acetone in dimethyl formamide and the glycol, is dispersed into the dispersion form of fine solid particles, or is dissolved in the high boiling solvent, are dispersed in the hydrophilic adhesive subsequently, and apply subsequently.But these auxiliary developer precursors self in conjunction with or be used in combination with auxiliary developer.

Color silver halide photographic-material of the present invention preferably comprises aforementioned auxiliary developer as electron transfer agent.Preferred electron transfer agent comprises, for example, is described in general formula (ETA-1) or the above-claimed cpd (ETA-2) of JP-A 2002-23296.The object lesson of these compounds comprises and is described in JP-A 2000-19698, the compound of 0157-0159 joint.

The trapping agent of the oxidation product of developer

Color silver halide photographic-material of the present invention preferably comprises and can react the compound that forms colourless basically material by the oxidation product with color developer.

Especially, the polymerizable compound that preferably has the repetitive of the monomer of representing derived from following structural formula (I):

Formula (I)

Wherein, R ¹Be hydrogen atom or alkyl, X is the essential atomic radical that forms assorted cyclic rings;

Compound with following structural formula (II) expression:

Formula (II):

Wherein, R ¹Be can substituted alkyl, naphthenic base, alkenyl, aralkyl, aryl or heterocyclic group; X is the essential atomic radical that forms assorted cyclic rings, and prerequisite is to select

Assorted cyclic rings is so that have and be no more than 8 pKa; N is 0 or 1; And

The compound of following structural formula (III) expression:

Formula (III): R ¹-(B ¹) _n-A ¹-O-A ²-(B ²) m-R ²

Wherein, R ¹And R ²Be substituted alkyl, aryl, aralkyl or heterocyclic group, or R ¹And R ²Can be bonded to each other to form ring; A ¹And A ²Be carbonyl or sulfonyl; B ¹And B ²Be oxygen atom or N-R, wherein R is hydrogen atom or alkyl; N and m are 0 or 1.

The example of aforesaid compound comprises and is described in JP-A 01-193855,01-283559,01-283558, the compound of JP-B 4-73722 and patent 2699005.These compounds can add emulsion layer or not comprise the middle layer of emulsion.

Thermal treatment

In an embodiment preferred of the present invention, photographic material of the present invention is carried out thermal development.By heating former state photographic material or handle material with other and heat and carry out thermal development.Handling material is a kind of sheet material of describing after a while that has the processing layer that comprises alkali and/or alkali precursor on carrier.Processing layer preferably comprises hydrophilic adhesive.After the imaging exposure, photographic material heats to carry out image formation with handling material, and the photosensitive layer surface layer with photographic material is pressed onto on the processing aspect of handling material simultaneously.Preferably, after water is supplied to photographic material or handles material with maximum swelling photographic material and the 1/10-30 amount doubly of handling the required water of all layers of material, with photographic material with handle the material lamination and colour development is carried out in heating.Aforementioned auxiliary developer can optionally be included in photographic material or handle in the material or with water and apply on it.

The thermal treatment photographic material is that conventional known and photographic material of photographic art and technology thereof for example are described in detail in " Shashin-Kogakuno KISO " (photograph engineering foundation, 1970, CoronaCo.) 553-555 page or leaf; Nebletts takes a picture and duplicates handbook, the 7th edition (Van Nostrand and Reinhold Company), 32-33 page or leaf; United States Patent (USP) 3,152,904,3,301,678,3,392,020 and 3,457,075; BrP 1,131,108 and 1,167,777; And RD17029 (1978, June) 9-15 page or leaf.Heating-up temperature in the thermal development is 50-250 ℃ and preferred 60-150 ℃.

In order to promote thermal development, hot solvent can add photographic material.Hot solvent is meant a kind of compound that can heat liquefaction and promote image formation.Hot solvent be preferably white and under typical temperature, be solid, preferably not too volatile in addition.Fusing point is preferably 70-170 ℃.Its example comprises and is described in United States Patent (USP) 3,347,675 and 3,667, and 959 polar organic compound.Object lesson comprises amide derivatives (as, benzo acid amides), urea derivative (as, methyl urea, ethylidene-urea), the sulfonamide derivant (as, be described in the compound of JP-B 1-40974 and 4-13701), polyvalent alcohol anhydro sorbitol, and polyglycol.Can be used for other hot solvent of the present invention comprises and is described in United States Patent (USP) 3,347,675,3,438,776,3,666,477 and 3,667,959; RD 17643; JP-A51-19525,53-24829,53-60223,58-118640,58-198038,59-68730,59-84236,59-229556,60-14241,60-191251,60-232547,61-52643,62-42153,62-44737,62-78554,62-146645,62-139545,63-53548,63-161446; JP-A1-224751,1-227150,2-863, the compound of 2-120739 and 2-123354.In addition, the example of preferred hot solvent is to be described in JP-A 2-297548, and 8 pages upper left to 9 pages of upper left compound TS-1 to TS-21.The aforementioned hot solvent can be used in combination.

In photographic material and/or processing material, alkali or its precursor are preferred for promoting silver to develop or dyestuff forms reaction.The alkali precursor comprises, for example, can be when heating organic bronsted lowry acids and bases bronsted lowry of decarboxylation salt and a kind of can be by nucleophilic displacement of fluorine in the molecule, Lessen resets or Beckmann arranges and discharge the compound of amine.Its object lesson is described in United States Patent (USP) 4,514, and 493 and 4,657,848; " Kochigijutsu (known technology) the 5th phase (on March 22nd, 1991 was published by Azutech Co.) 55-86 page or leaf.A kind of method that is used to produce alkali of also preferred employing, wherein the alkaline metal cpds with slightly water-soluble can combine in the water as medium with the compound (being also referred to as complex compounds) of the metallic ion formation complex that forms this alkaline metal cpds with a kind of.This method that is used to generate alkali is described in European patent 210,660 and United States Patent (USP) 4,740,445.In this case, the alkaline metal cpds with slightly water-soluble adds photographic material and can handle material with compound (the being also referred to as complex compounds) adding of the metallic ion formation complex that forms this alkaline metal cpds.This formation preferably increases the storage stability of photographic material.

Handle material

Except introducing above-mentioned alkali and/or its precursor, being used for the heat-developed processing material of the present invention has in thermal development process shroud air, prevent that material from evaporating from photographic material, will the material that is used for handling except that alkali be supplied to photographic material or remove after developing unwanted composition (as yellow filter dyestuff and anti-halation dyestuff) or the function of the non-required component that produces at developing process.Color developer and/or its precursor can be added the processing material.Handle material and can have the function of the desilverization.For example, handle on the material dissolving a part or all silver halide and/or developed silver, can be included in as the fixer of the solvent that is used for silver halide and handle material if the photographic material of exposure is placed on.

The cementing agent that is used to handle material and carrier can be used for the identical of photographic material.The processing material can add has mordant to remove above-mentioned dyestuff.Can use photographic art known mordant usually.Its example comprises and is described in United States Patent (USP) 4,500,626 hurdle 58-59, JP-A61-88256, the 32-41 page or leaf, JP-A 62-244043 and 244036 those.Can use to be described in United States Patent (USP) 4,463 079 dyestuff-acceptance polymer compound.Can comprise the aforementioned hot solvent.

The processing layer of handling material can comprise alkali or its precursor.Can use any organic base and inorganic base.The example of inorganic base comprise alkaline metal or alkaline earth metal hydroxide (as, potassium hydroxide, NaOH, lithium hydroxide, calcium hydroxide, magnesium hydroxide), phosphate (as, the second month in a season and uncle's phosphate such as dipotassium hydrogen phosphate, sodium hydrogen phosphate, and sodium ammonium biphosphate), carbonate (as, sal tartari, sodium carbonate, sodium bicarbonate, magnesium carbonate), borate (as, potassium borate, sodium borate, kodalk); Acylate (potassium acetate, sodium acetate, potassium oxalate, sodium oxalate, potassium tartrate, sodium tartrate, natrium malicum, sodium palmitate, odium stearate); With alkaline metal or earth alkali metal acetylide, for example be described in JP-A63-25208.

The example of organic base comprises ammonia, aliphatic series or aromatic amine, as primary amine (as, methylamine, ethamine, butylamine, just-and hexylamine, cyclohexylamine, 2 ethyl hexylamine, allyl amine, ethylenediamine, 1, the 4-diaminobutane, hexane diamine, aniline, anisidine, para-totuidine, alpha-naphthylamine, m-phenylene diamine, 1, the 8-diaminonaphthalene, benzylamine, phenethyl amine, monoethanolamine), secondary amine (as, dimethyl amine, diethylamide, dibutylamine, diallylamine, methylphenylamine, N-methyl-benzyl amine, N-methylethanolamine, diethanolamine), tertiary amine (as, N-methylmorpholine, N-hydroxyethyl morpholine, the N-methyl piperidine, N-ethylpiperidine, N-hydroxyethyl piperidine, N, N '-lupetidine, N, N '-dihydroxy ethyl piperidines, diazabicyclo [2,2,2]-and octane, N, N-dimethylethanolamine, N, N-dimethyl propanol amine, N-methylethanolamine, N-methyl dipropanolamine, triethanolamine, N, N, N ', N '-tetramethylethylenediamine, N, N, N ', N '-tetrahydroxyethyl-ethylene diamine, N-methylpyrrole and pyridine (N-methylpyrrolodine), polyamines (as, diethylene triamine, trien, polyethylene imine based, PAH, polyvinyl benzyl amine, poly--(methacrylic acid N, the N-lignocaine ethyl ester), poly--(N, N-dimethyl vinyl benzyl amine)), hydroxyl amine (as, hydramine, N-hydroxy-n-methylaniline), heterocyclic amine (as, pyridine, lutidines, imidazoles, aminopyridine, N, the N-dimethyl aminopyridine, indoles, quinoline, isoquinoline, poly--4-vinylpridine, P2VP), narrow (as, singly narrow and narrow, imidazotane, glyoxal ethyline as acetyl, 1,4,5, the 6-tetrahydropyrimidine, the 2-methyl isophthalic acid, 4,5, the 6-tetrahydropyrimidine, 2-phenyl-1,4,5, the 6-tetrahydropyrimidine, the imino group piperidines, diazabicyclo-nonene, the diazabicyclo hendecene), two, three or four narrow guanine (as, water-soluble mono guanine such as guanine, dimethylguanine, tetramethyl guanine) 2-aminooimidazole quinoline, 2-amino-1,4, the 5-tetrahydropyrimidine), for example be described in JP-A 62-170954; Soluble single or two guanines of water, two, three or four guanidines, quaternary ammonium hydroxide (as, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TBAH, trimethyl benzyl amine-oxides, trioctylphosphine methyl oxidation ammonium, the methyl hydrogen pyridine oxide), for example be described in JP-A63-70845.

Be used for the alkali precursor if will be used for (or cooperate) compound of formation complex of metallic ion of the alkaline metal cpds of slightly water-soluble, can use amino carboxylic acid such as ethylenediamine tetraacetic acid, nitrilotriacetic acid and diethylene-triamine pentaacetic acid or its salt; Aminophosphonic acid and its salt; Pyridine radicals carboxylic acid or its salt such as 2-pyridine carboxylic acid, pyridine-2,6-dicarboxylic acid and 5-ethyl-2-pyridine carboxylic acid; With iminodiacetic acid and its salt such as benzyl iminodiacetic acid and α-picolyl iminodiacetic acid.The compound that forms complex is preferably to be used by the salt form of organic base such as guanidine or alkaline metal neutralization.Alkali or its precursor are preferably with 0.1-20g/m ²And more preferably 0.5-10g/m ²Amount add to handle material.

Alkali or its precursor can add photographic material.If the alkaline metal cpds of slightly water-soluble adds photographic material, preferably use metal hydroxides or metal oxide, and zinc hydroxide and zinc paste are especially preferred.

In using the thermal development of handling material, preferably use a spot of water (also being expressed as water-bearing media) to promote to develop, handle the transfer of composition or the diffusion of non-required material.Particularly, if with the alkali compounds of slightly water-soluble with can be used in combination with the complex compounds that the metallic ion of alkali compounds forms complex, water is necessary.Water can comprise inorganic alkaline metal salt, organic base, and low boiling point solvent, surfactant, antifoggant can form compound, mould resistant or the germifuge of complex with the metallic compound of slightly water-soluble.Can use the water of any general use.Its example comprises distilled water, tap water, well water and mineral water.Using photographic material and handling in the material hot treatment device, water is discardable or reuse by recovery.Under one situation of back, use the water that comprises the composition that from material, leaches.Can use to be described in JP-A63-144354 63-144355, the device of 62-38460 and 3-210555 or water.Water can be provided to photographic material or handle one of material or both.The amount of providing of water is 1/10-30 (preferred 1/10-1) times that makes photographic material and handle all layers maximum swelling aequum except that its backing layer of material.Preferred use for example is described in JP-A 62-253159, and the method for 5 pages and JP-A 63-85544 is to provide water.Solvent can be included in the microcapsules.In addition, water can hydrate forms be included in photographic material handle material or both in.The temperature of the water that is provided is 30-60 ℃, for example is described in JP-A 63-85544.

Annealing device

Usually known heating arrangement can be used for thermal development photographic material of the present invention.Its example comprises the system that contacts with heat hot piece or face well heater, and the system that contacts with warm-up mill or drum with system infrared or that the far-infrared lamp well heater contacts, can be passed the system of maintenance atmosphere at high temperature and the system of using high-frequency to heat.

In addition, provide the conductive layer that comprises generation heat,, wherein will encourage the Joule heat that produces to be used to carry out thermal development as the backing layer of silica aerogel layer at the back side of photographic material or processing material.Can use the heating element that is described in JP-A 61-145544.Photographic material can a kind ofly for example be described in JP-A 62-253159 and 61-147244, and 27 pages mode overlaps wherein photosensitive layer on the processing material of processing layer.Heating-up temperature is preferably 43-100 ℃.

Usually known annealing device can be applicable to color imaging method of the present invention.Its preferred example comprises and is described in JP-A 59-75247,59-177547,59-181353,60-18951,62-25944,6-130509,6-95338,6-95267, the device of 8-29954 and 8-29955.Also have commercial device, as Pictrostatt 100, Pictrostatt 200, and Pictrostatt 300, and Pictrostatt 330, and Pictrostatt 50, Pictrography 3000 and Piotrography 2000 (all deriving from Fuji Film Co.Ltd.).

Thermal development, the desilverization and photographic fixing

In color imaging method of the present invention, be included in development in the treatment element and stop agent and can play a role simultaneously with developing.Develop stop agent being meant a kind of have can be finishing suitable development after by alkali neutralization or reduce alkali concn in the layer suppressing the compound of development with alkali reaction, or a kind of compound that can suppress to develop by interaction with silver or silver salt.Its object lesson comprises the acid precursors that can discharge acid in when heating, and electrophilic compound maybe can heat and causes and the compound of the substitution reaction of the alkali that coexists nitrogen-containing compound and sulfhydryl compound or its precursor.More specifically, these substance descriptions are in JP-A 62-253159, the 31-32 page or leaf.In addition, wherein comprise the mercaptan carboxylic acid's who for example is described in JP-A 8-56062 zinc salt and wherein to use the combination of the treatment element of the complex compounds of early describing also be favourable.Similarly, printing off (print-out) prevents that agent can be included in the treatment element and brings into play its function simultaneously with developing.Print off the example that prevents agent and comprise the single halogen compounds that is described in JP-B 54-164, be described in three halogen compounds of JP-A 53-46020, for example be described in the many halogen compounds that for example are expressed as tetrabromo dimethylbenzene that are connected to the compound of the halogen on the aliphatic carbon atom comprising of JP-A 48-45228 and are described in JP-B 57-8454.Development restrainer such as 1-phenyl-5-mercapto-tetrazole are effectively, for example are described in BrP 1,005,144.Viologen (viologen) compound that is described in JP-A8-184936 also is effective.Print off the consumption preferably 1 * 10 that prevents agent ^-4-1mol/mol Ag and more preferably 1 * 10 ^-3-1 * 10 ^-1Mol/mol Ag.

In thermal process of the present invention, the developed silver that produces in the thermal treatment of photographic material can be by allowing to that the oxygenant that is used for silver as the developed silver bleaching agent is comprised and in developing reaction or play a role subsequently and remove.In addition, finish development with after forming image, second material that will comprise the oxygenant that is used for silver and photographic material lamination are with removal developed silver.

The conventional silver-colored bleaching agent that uses can be used as and is used for the bleaching agent that the present invention handles material.These bleaching agents are described in United States Patent (USP) 1,315, and 464 and 1,946,640, and photograph chemistry, 12 volumes, 30 chapters, (Foundation Press, London, England).These bleaching agents effectively the silver oxide image to dissolve them.The example of effective silver-colored bleaching agent comprises alkaline metal two chromate and the alkaline metal ferricyanide.Particularly, preferred silver-colored bleaching agent is water miscible, comprise, for example, triketohydrindene hydrate, indandione, six ketone siloxane, 2,4-dinitrobenzoic acid, benzoquinones, benzene sulfonic acid and 2,5-dinitrobenzoic acid.Also comprise metal complex salts such as cyclohexyl dialkyl amido tetraacethyl iron (III) salt, ethylenediamine tetraacetic acid iron (III) salt, and ferric citrate (III) salt.For being used for second cementing agent of handling material, carrier and other adjuvant can use and be used to handle material (first handles material) identical materials.

The coating weight of bleaching agent can change along with the silver-colored coverage of the overlapping photographic material of want, 0.01-10mol normally, preferred 0.1-3mol and more preferably 0.1-2mol/mol silver coverage/unit area.

Compound with photographic fixing ability can be included in to be handled in the material to remove the silver halide that becomes non-required after finishing image formation.The object lesson of this system comprises that wherein physical development nuclei and ag halide solvent allow to be included in to be handled in the material, thereby silver halide is dissolved in heating process in the photographic material so that it is fixed in the processing layer.On physical development nuclei, reduce to form physical development silver-colored and be fixed in the processing layer by the silver halide of the dissolving like this of photographic material diffusion.Usually known physical development nuclei is arranged, comprise, for example, heavy metal such as zinc, mercury, lead, cadmium, iron, chromium, nickel, tin, cobalt, copper, and ruthenium, noble metal such as palladium, platinum, the colloidal solid of silver-colored and golden and chalcogen compound such as sulphur selenium and tellurium.These physical development nuclear materials can make the corresponding metal ion be reduced agent such as ascorbic acid, sodium borohydride and p-dihydroxy-benzene reduction form the metallic colloid dispersion, or solvable sulfide, selenide, or metallic ion mixes formation by the soluble metal sulfide of water, the acquisition of the form of the aqueous colloidal dispersion that metal selenide or metal telluride are formed with telluride solution.Dispersion preferably forms in hydrophilic adhesive such as gelatin.The preparation of collargol particle is described in United States Patent (USP) 2,688,601.Can optionally carry out desalination to remove excessive soluble salt, this is that silver halide emulsion is made known.Physical development nuclei is preferably dimensioned to be 2-200nm.Physical development nuclei is preferably with 1 * 10 ^-3-100mg/m ²And more preferably 1 * 10 ^-2-10mg/m ²Amount be included in the processing layer.Separately prepare physical development nuclei and add coating solution.In addition, for example, with nitrate and sodium sulphide, or chlorauride and reductive agent react in comprising the solution of hydrophilic adhesive.The preferred example of physical development nuclei comprises silver, silver sulfide and palladium sulfide.

If photographic fixing silver halide in aforementioned system need make a kind of reductive agent of physical development that can cause be present in the layer that comprises physical development nuclei.The reductive agent of non-diffusion need add this layer.But diffusible reductive agent can add photographic material and handle any layer of material.As reductive agent, can use the auxiliary developer of early describing with this function.In addition, silver halide can not use physical development nuclei or reductive agent and photographic fixing.Therefore, use so-called ag halide solvent, carry out the salt displacement to form the insensitive silver salt of light at silver ion.

In any case above-mentioned, can use usually known ag halide solvent, as be called the compound of silver-colored solvent or fixer.Its example comprises thiosulfate, sulphite, thiocyanate, sulfide compound are as 1, and 8-two-3,6-two thiophene octanes or 2,2 '-thiodiethanol, 6,9-two oxa-s-3,12-two thiophene four decane-1, the 14-glycol contains compound such as the uracil or the hydantoins of 5-or 6-unit imido basic ring, for example is described in JP-A 8-179458, sulfhydryl compound, the sulfo-uracil has the nitrogen-containing heterocycle compound of sulfide group, for example is described in JP-A4-365037,11-21 page or leaf and be described in the compound that is expressed as general formula (1) of JP-A 53-144319.Can use mercaptan trimethyl triazole or internal compensation-ion thiol salinization compound, be described in Analytica Chemica Acta, volume 248,604-614 page or leaf (1991).What for example be described in JP-A8-69097 can also can be used as ag halide solvent with the compound that carries out its stabilization by the photographic fixing silver halide.In addition, can use for example be described in United States Patent (USP) 2002/9678 be different from soluble fixer under the temperature of development.These ag halide solvents can be used in combination.In aforesaid compound, sulphite and contain the compound of 5-or 6-unit imido basic ring such as uracil or hydantoins are preferred.Particularly, the introducing advantageous embodiment of the uracil of potassium salt form or hydantoins the gloss decline after the raw material of handling material is preserved.

The total content of ag halide solvent in processing layer is preferably 0.01-100mmol/m ², more preferably 0.1-50mmol/m ²And further more preferably 1-30mmol/m ²With the mol ratio of the silver-colored coverage of photographic material 1/20-20 preferably, more preferably 1/10-10 and further more preferably 1/3-3.Ag halide solvent can be by at solvent such as water, methyl alcohol, and ethanol, acetone, dimethyl formamide, or methyl propyl diol or the solution in aqueous bases or acid, or add coating solution with the form of solid particulate dispersion.

Handle material and preferably have at least one timing layer.Timing layer helps to postpone to bleach or the anticipation reaction of photographic fixing reaction between silver halide and developer finished basically, reacts with colour coupler subsequently.Timing layer can be by gelatin, polyvinyl alcohol (PVA), or poly-[(vinyl alcohol)-altogether-(vinyl acetate)] formed.This layer can be isolated timing layer, for example is described in United States Patent (USP) 4,056,394 and 4,061,496.

In color imaging method of the present invention, can be with at least two kinds of processing materials with standalone feature, as carry out first of colour development and handle material and bleach and/or second the handling material and be successively placed on the photographic material to obtain thermal treatment of photographic fixing.In this case, preferably, the processing material that carries out colour development does not comprise can be bleached and/or the compound of photographic fixing as mentioned above.Photographic material is placed on first handles on the material, be placed on second subsequently and handle material, make the photosensitive layer of photographic material towards second processing layer of handling material to bleach to carry out thermal development.In this case, water is supplied to photographic material or handles material with the 0.1-30 amount doubly of all layers aequum except that the backing layer of swelling photographic material and processing material.Heating 5-60 under temperature is 40-100 ℃ handles to bleach with photographic fixing second with this state.The amount or the kind of similar water in the time of can adopting and handle material and develop, the method for water is provided and photographic material is stacked the method for handling on the material.

Appreciate with standing storage or vision in order after handling, to adopt photographic material, preferably photographic material is carried out at least a following processing that is selected from: the technology that is used to remove silver halide, bleaching or photographic fixing and be used to remove the technology of the insensitive silver compound of light as described above.At this, the insensitive silver compound of light is meant developed silver, collargol or organic silver salts.If photographic material is read to change into electronic image, then nonessential bleaching or photographic fixing technology by scanner after handling.But preferably carry out photographic fixing technology.In addition, if the colour negative of handling is back to the consumer as recording medium, for example be described in United States Patent (USP) 2002/18944, WO 01/96943,01/96945 and 01/96947, the image of thermal development photographic material is read by scanner, and preferably, image is read by scanner once more in bleaching or after fixing.This is because having the residue silver halide that absorbs and become noise source when scanner reads in visible wavelength region influences the gained electronic image unfriendly.In order to obtain a kind ofly to develop and the simplification technology of not photographic fixing separately, preferably use laminar silver halide grain or silver chloride crystal grain.Preferably use the silver-colored coverage that for example is described in United States Patent (USP) 2002/12887 low silver-colored photographic material in addition as 0.1-4.5.In addition, the also preferred photographic material that is substantially free of colour former agent that adopts.

Other material

In photographic material of the present invention or processing material, can use various surfactants to be used for coating additive, to peel off or lubrication modifier, antistatic agent or acceleration are developed.The object lesson of surfactant is described in " Kochigijutsu (known technology) the 5th phase (on March 22nd, 1991, by Azutech Co. publish) 136-138 page or leaf and JP-A 62-173463 and 62-183457.Photographic material can add Organic fluoride-compound.The representative example of Organic fluoride-compound comprises fluorinated surfactant, as is described in JP-B 57-9053,8-17 hurdle and JP-A 61-20944 and 62-135826; Oily fluorochemicals such as fluorinated oil and solid fluororesin such as tetrafluoroethene.

Photographic material and processing material preferably have lubricity.Lubricant is included in the two sides of photosensitive layer and backing layer.Term " preferably has lubricity " and is meant that dynamic friction coefficient is 0.01-0.25.Dynamic friction coefficient is defined as when in resulting value during with speed 60cm/min (under the atmosphere at 25 ℃ and 60%RH) transmission on the stainless steel ball of 5mm diameter.The example of preferred lubricant comprises polysiloxane, the ester of higher fatty acid amides and higher fatty acid and higher alcohol.The object lesson of polysiloxane comprises dimethyl silicone polymer, poly-di-ethyl siloxane, polystyrene methyl siloxane and PSI.Wherein, polymethyl siloxane is especially preferred with the ester that comprises chain alkyl.Lubricant is preferably the outermost layer that adds on emulsion layer side or the backing layer.

Photographic material of the present invention or processing material preferably comprise antistatic agent.The example of antistatic agent comprises carboxylic acid or carboxylate, contains the polymkeric substance of sulfonate, cationic polymer and ionic surface active agent compound.Preferred antistatic agent is to be selected from ZnO, TiO ₂, SnO ₂, Al ₂O ₃, In ₂O ₃, SiO ₂, MgO, BaO, MoO ₃, and V ₂O ₅At least a.Especially preferred is to have to be no more than 10 ⁷Ω cm and more preferably no more than 10 ⁵The volume resistance of Ω cm and particle size are 0.001-1.0 μ m's (Sb, P, B, In, S, Si, fine grained crystal metal oxide C) or its composite oxides.Antistatic agent is preferably with 5-500mg/m ²And more preferably 10-350mg/m ²Amount add photographic material.The ratio of this conduction crystalline oxides or its composite oxides and cementing agent preferably 1: 300-100: 1 and more preferably 1: 100-100: 5.

In the composition of photographic material and processing material, preferably include various polymer emulsions to improve the physical property of this layer, as dimensional stability, coiling-resistant and anti-adhesiveness, cracking, or pressure-sensitive or desensibilization.The object lesson that can be used for polymer emulsion of the present invention comprises and is described in JP-A62-245258, those of 62-136648 and 62-110066.

Particularly, has the cracking that the introducing of polymer emulsion in mordant layer of hanging down glass transition point (for example, not being higher than 40 ℃) prevents this layer.On the other hand, the application of polymer emulsion in backing layer with higher glass transition point can prevent to curl.

Photographic material or processing material preferably comprise matting agent.Matting agent can add any emulsion layer side and backing layer side and the preferred outermost layer that adds the emulsion layer side.Matting agent can be dissolve in Treatment Solution a kind of or insoluble a kind of, but preferred combination is used.For example, particle gathers (methyl methacrylate), and particle poly-(methyl methacrylate/methacrylic acid=9/1 or 5/5 mol ratio) and particle polystyrene are preferred.The particle size of matting agent is 0.8-10 μ m preferably.Narrow particle size distribution is preferred, and at least 90% total particle number preferably falls in the 0.9-1.1 scope doubly of average particle size particle size.Its example comprises polymethylmethacrylate (0.2 μ m), poly-(methyl methacrylate/methacrylic acid=9/1 mol ratio, 0.3 μ m), and polystyrene (0.25 μ m).Its other object lesson is described in JP-A 61-88256,29 pages.Also can use the compound that is described in JP-A63-274944 and 63-274952, as the benzoguanamine resin bead, polycarbonate resin bead and ABS resin bead.Also can use and be selected from the compound of mentioning those morning among the described Research Disclosure.

Film forms

The film loader that is used to pack photographic material is below described.The main material that is used for film loader of the present invention can be metal or synthetic plastic.The example of preferred plastic material comprises polystyrene, tygon, polypropylene and polyphenylene ether.The box material can comprise various antistatic agent.Preferred antistatic agent comprises carbon black, metal oxide particle, nonionic, negative ion, kation or betaine type amphoteric surfactant and polymer beads.These antistatic boxes for example are described in JP-A1-312537 and 1-312538.Resistance under 25 ℃ and 25%RH preferably is no more than 10 ¹²Ω.Plastic casing is usually by using the plastics that mix with carbon black that is used for shading or pigment to make.Box can be the 135-size.With the 25mm reduced size of 135mm size box to 22mm or lower, to carry out the microminiaturization of camera effectively.The internal volume of box is no more than 30cm ³And preferably be no more than 25cm ³The weight of box is 5-15g preferably.The box that can use film wherein to advance by rotating bobbin.The top that also can use the film that wherein is contained in box inside is the box that advances by rotating bobbin on the film working direction.Box with this structure is described in United States Patent (USP) 4,834, and 306 and 5,225,613.

Photographic material of the present invention also can be packaged in the packing film of commercially available camera lens coupling.For example, photographic material can be packaged in the packing film of the camera lens coupling that is described in Japanese patent application 10-158427 and JP-A 11-352564 and 2000-19607.

Outside at the packing film of film loader or camera lens coupling indicates adoptable technology in advance and for example " is used for thermal treatment " or clearly provides the handling of paying in advance.

In the present invention, the processing stage waste material that produces or waste liquid can be used as resource and reclaim.Particularly, if obtain digital image information, can carry out resource from photographic material effectively and reclaim by the photographic material that uses scanner to read processing.In this case, can reclaim the almost silver compound of the adding photographic material of total amount, this utilization more friendly to environment and expensive raw material is best.

In the system of the photographic material that can in reclaiming photograph developing machining experiment chamber, accumulate or in the treatment facility or transmitting the photographic material that callable photographic material recycled to the system of the company that recycles.

In the present invention, recycled materials mainly are the silver from photographic material.After this recovery of silver will be described.In order to retrieve silver, can therefrom can reclaim silver fully with the photographic material desilverization to obtain to contain the solution of soluble silver salt from the photographic material of handling.In this case, recyclable silver keeps the form of film simultaneously, and this is favourable to separating as the silver that reclaims resource from base.The state that also can silver-colored partly or entirely be retained in the photographic material carries out the resource recovery.The known method of separating or reclaim silver from the solution that contains soluble silver salt is arranged usually.Its example comprises the method that wherein makes the base metal with ionization trend bigger than silver contact the silver that dissolves with replacement with solution, and the electrolytic process of wherein coming depositing silver by electrolysis.Electrolytic silver reclaims and for example is described in JP-A 50-98837,52-26315,52-115723,53-32869 and 53-60391; Deutsche Bundespatent 2,333,018 and 2,429,288; Belgian patent 780,623, United States Patent (USP) 3,400 is in 056,3,840,0563,3,964,990 and 4,069,127.Wherein said method comprises wherein along with potential change adds reductive agent to carry out the method for electrolysis, adopts phrenic method, electrodialysis, the method for Control current and the technology that is used to improve solution supply, stirring and equipment such as electrode or battery lead plate automatically.

Except aforesaid silver recovery method, also adopt deacidite, for example be described in JP-A 49-70823 and 51-17114; Deutsche Bundespatent 2,630,661.In addition, the present invention can with the silver recovery method comprise electrolytic process (being described in French Patent (FRP) 2,299,667), the precipitation method (are described in JP-A 52-73037 and Deutsche Bundespatent 2,331,220), ion exchange process (is described in Deutsche Bundespatent 2,548,237) and metal replacement method (being described in BrP 1,353,805).

The ion exchange resin that can be used in the aforementioned ion exchange process is anion exchange resins, and wherein the functional group of this resin is connected on the three-dimensional polycondensation polymeric matrix.The example of polymeric matrix comprises the SDVB multipolymer, methacrylic acid or acrylic acid and divinyl benzene copolymer, and phenolics.Described functional group for example is quaternary ammonium group or uncle's tertiary ammonium salt structure.Chelating resin comprises Iminodiacetate, Polyamine Type, amidoxim type, phosphoramidic acid type, pyridine type and aminodithioformic acid type.Aforementioned ion exchange resin also can be commercially available, as the Diaion (trade name) of Mitsubishi Chemical Corp., the Amberlite of ORGANO CORP., Duolite and the Sumikaion of SUMITOMO CHEMICAL Co.LTD..The object lesson of anion exchange resins comprises:

(i) strong-base anion-exchange resin, as Mitsubishi Diaion SA-11A, Mitsubishi Diaion PA-308, Mitsubishi Diaion SA-20A, MitsubishiDiaion SA-21a and Mitsubishi Diaion PA-408;

(ii) weak-base ion-exchange resin, as Mitsubishi Diaion WA-10, Mitsubishi Diaion WA-11, Mitsubishi Diaion WA-20, MitsubishiDiaion WA-21 and Mitsubishi Diaion WA-30.The anion substituent of aforementioned deacidite is specifically restriction not, and preferred example comprises OH ^-, Cl ^-, SO ₄ ^2-, Br ^-, COO ^-, CO ₃ ^2-And SO ₃ ^2-In aforementioned anion exchange resins, weak-base ion-exchange resin is preferred in the present invention.

Exposure method

If photographic material of the present invention, uses camera directly take pictures landscape or personage usually as the camera material.Be packaged in the situation in the packing film of camera lens coupling comprising photographic material.In addition, in following exposure, adopt described photographic material: use printer or amplifier to carry out the exposure of reversible film or negative film; Use the exposure device of copy machine to carry out the scan exposure original drawing by slit; By make light emitting diode or various laser instrument (as, laser diode, gas laser) according to image information and electric signal emission carrying out scan exposure (for example be described in JP-A 2-129625,5-176144,5-199372,6-127021); With directly expose or by image display such as CRT liquid crystal display, the optics system output image information on electroluminescent display or the plasma scope and exposing.

The example that is used for the light source of document image on photographic material comprises natural light, tungsten lamp, light emitting diode, laser light source, CRT light source and be described in United States Patent (USP) 4,500,626 and the light source of JP-A2-53378 and 2-54672.Also can use the wavelength conversion elements and carry out the imaging exposure in conjunction with nonlinear optical material and coherent source such as laser optical.Nonlinear optical material is meant the material that can show Nonlinear Electric Field and unpolarizing when applying high light electric field such as laser.Its example comprises mineral compound such as lithium niobate, potassium dihydrogen phosphate (KDP), lithium iodate, and BaB ₂O ₄, urea derivative, nitroaniline derivant, nitropyridine-N-oxide derivative such as 3-methyl-4-nitropyridine-n-oxide (POM) and be described in the compound of JP-A 61-53462 and 62-210432.Wavelength conversion elements known in the art comprises monocrystal guide type and fibrous type, and the both is useful.

As above-mentioned image information, the picture signal that employing obtains by video camera or electronic still camera, TV signal such as Nippon Television signal standards (NTSC), by original drawing being divided into picture signal that a large amount of picture element obtain and by using a computer, as CG and CAD and the image that produces.

Scanner reads

In the present invention, the gained image can use scanner to read and change into electronic image information.Scanner is meant that photographic material wherein will reflect by optical scanning or transmission density changes into the equipment of image information.Usually be different from direction on the direction of photographic material moving direction by opticator and move and the desired part of scanography material scanner.

In addition, photographic material can be fixed in the opticator of motion scan instrument only, or this opticator can only fixed in the mobile photographic material.Its combination also is feasible.

In order to read the image information of photographic material, preferably by wavelength is carried out the amount of overall exposure or next definite reflection of slit scan exposure or transmission light at least corresponding to the light of the corresponding absorption of three kinds of dyestuffs.In this case, preferably use scattered light rather than directional light to remove the information that causes by the crackle in matting agent or the film.Also preferably light accept to use in the part semiconductor image sensor (as, area-type CCD, CCD line-sensor).For example be described in United States Patent (USP) 5,465, it also is feasible that 155,5,519,510 and 5,988,896 image forms, and developed silver image that wherein forms in photographic material or Infrared dyes image use infrared light detection to form image.United States Patent (USP) 2001/31144,2001/52932 and 2001/43812 discloses, by the imaging in conjunction with the image that is read by as seen corresponding and infrared scanner.

The view data that so obtains can be used various image display equipment and manifest.Can use any image display equipment, comprise colour or monochromatic CRT, liquid crystal display, plasma emission display and EL display.

The picture signal that so reads is exported to form image on recording materials.Not only use photographic silver halide material but also use other material output image.Also can adopt various hard copy devices with output image, comprise ink-jet systems, the hot transfering system of subliming type, electric photograph system, Cycolor system, hot autochrome, expose system and silver halide thermal photographic system to silver-halide color paper.Any aforementioned system can demonstrate effect of the present invention.

Fundamental purpose of the present invention is to introduce the image information that obtains by development, and such numerical data and photograph information optics in a conventional manner output on printing material such as the photograph autochion printing paper.

Embodiment

Describe the present invention according to embodiment, but embodiment of the present invention is in no way limited to these.

Embodiment 1

The preparation of color silver halide photographic-material

The preparation of sample 101

Thick at 96 μ m, on the bottom polyethylene terephthalate film carrier vector, form have show down composition with lower floor with preparation multi layer colour photographic material sample 101.The ISO speed of the sample of measuring according to the method for ANSIPH2.27 101 is 400.The addition of every kind of compound is expressed as g/m ²Unless, refer else.The scale that the amount of silver halide or collargol changes into silver amount and sensitizing dyestuff (being expressed as " SD ") is shown mol/Ag mol.Ground floor: anti-halation layer

The black collargol	???0.16
The black collargol	???0.16	??UV-1	???0.30
??CM-1	???0.12	??UV-1	???0.30
??CM-1	???0.12	Oil-1	???0.24
Gelatin	???1.33	Oil-1	???0.24

The second layer: middle layer

Iodine silver bromide latex emulsion i	???0.06
Iodine silver bromide latex emulsion i	???0.06	??AS-1	???0.12
Oil-1	???0.15	??AS-1	???0.12
Oil-1	???0.15	Gelatin	???0.67

The 3rd layer: the low speed red-sensitive layer

Iodine silver bromide latex emulsion h	?0.19
Iodine silver bromide latex emulsion h	?0.19	Iodine silver bromide latex emulsion e	?0.17
SD-1	?2.22×10 ^-4	Iodine silver bromide latex emulsion e	?0.17
SD-1	?2.22×10 ^-4	SD-2	?3.72×10 ^-5
SD-3	?1.56×10 ^-4	SD-2	?3.72×10 ^-5
SD-3	?1.56×10 ^-4	SD-4	?3.41×10 ^-4
C-1	?0.77	SD-4	?3.41×10 ^-4
C-1	?0.77	CC-1	?0.006
Oil-2	?0.47	CC-1	?0.006
Oil-2	?0.47	AS-2	?0.002
Gelatin	?1.82	AS-2	?0.002

The 4th layer: the middling speed red-sensitive layer

Iodine silver bromide latex emulsion b	?0.41
Iodine silver bromide latex emulsion b	?0.41	Iodine silver bromide latex emulsion h	?0.19
SD-1	?3.46×10 ^-4	Iodine silver bromide latex emulsion h	?0.19
SD-1	?3.46×10 ^-4	SD-2	?2.44×10 ^-5
SD-4	?3.69×10 ^-4	SD-2	?2.44×10 ^-5
SD-4	?3.69×10 ^-4	C-1	?0.42
CC-1	?0.072	C-1	?0.42
CC-1	?0.072	DI-1	?0.046
Oil-2	?0.27	DI-1	?0.046
Oil-2	?0.27	AS-2	?0.003
Gelatin	1.45	AS-2	?0.003

Layer 5: high speed red-sensitive layer

Iodine silver bromide latex emulsion a	?0.63
Iodine silver bromide latex emulsion a	?0.63	Iodine silver bromide latex emulsion e	?0.07
SD-2	?1.35×10 ^-5	Iodine silver bromide latex emulsion e	?0.07
SD-2	?1.35×10 ^-5	SD-12	?2.43×10 ^-4
SD-4	?6.45×10 ^-5	SD-12	?2.43×10 ^-4
SD-4	?6.45×10 ^-5	C-2	?0.10
C-3	?0.17	C-2	?0.10
C-3	?0.17	CC-1	?0.013
DI-5	?0.024	CC-1	?0.013
DI-5	?0.024	DI-4	?0.022
DI-6	?0.010	DI-4	?0.022
DI-6	?0.010	Oil-2	?0.17
AS-2	?0.004	Oil-2	?0.17
AS-2	?0.004	Gelatin	?1.40

Layer 6: middle layer

????Y-1	????0.08
????Y-1	????0.08	????AS-1	????0.11
Oil-1	????0.17	????AS-1	????0.11
Oil-1	????0.17	????X-2	????0.005
Gelatin	????0.87	????X-2	????0.005

Layer 7: low speed green sensitive layer

Iodine silver bromide latex emulsion h	??0.17
Iodine silver bromide latex emulsion h	??0.17	Iodine silver bromide latex emulsion e	??0.071
??SD-14	??3.6×10 ^-5	Iodine silver bromide latex emulsion e	??0.071
??SD-14	??3.6×10 ^-5	??SD-15	??4.2×10 ^-4
??M-1	??0.375	??SD-15	??4.2×10 ^-4
??M-1	??0.375	??CM-1	??0.042
??DI-2	??0.010	??CM-1	??0.042
??DI-2	??0.010	Oil-1	??0.41
??AS-2	??0.002	Oil-1	??0.41
??AS-2	??0.002	??AS-3	??0.11
Gelatin	??1.21	??AS-3	??0.11

The 8th layer: the middling speed green sensitive layer

Iodine silver bromide latex emulsion b	??0.32
Iodine silver bromide latex emulsion b	??0.32	Iodine silver bromide latex emulsion h	??0.07
??SD-13	??3.7×10 ^-4	Iodine silver bromide latex emulsion h	??0.07
??SD-13	??3.7×10 ^-4	??SD-6	??3.44×10 ^-4
??SD-8	??1.05×10 ^-4	??SD-6	??3.44×10 ^-4
??SD-8	??1.05×10 ^-4	??M-1	??0.18
??CM-1	??0.042	??M-1	??0.18
??CM-1	??0.042	??CM-2	??0.044
??DI-2	??0.026	??CM-2	??0.044
??DI-2	??0.026	??DI-3	??0.003
Oil-1	??0.23	??DI-3	??0.003
Oil-1	??0.23	??AS-3	??0.046
??AS-4	??0.006	??AS-3	??0.046
??AS-4	??0.006	Gelatin	??1.01

The 9th layer: the high speed green sensitive layer

Iodine silver bromide latex emulsion a	??0.71
Iodine silver bromide latex emulsion a	??0.71	Iodine silver bromide latex emulsion e	??0.07
??SD-13	??8.0×10 ^-5	Iodine silver bromide latex emulsion e	??0.07
??SD-13	??8.0×10 ^-5	??SD-6	??3.42×10 ^-4
??SD-8	??1.04×10 ^-4	??SD-6	??3.42×10 ^-4
??SD-8	??1.04×10 ^-4	??M-1	??0.038
??M-2	??0.078	??M-1	??0.038
??M-2	??0.078	??CM-2	??0.010
??DI-3	??0.003	??CM-2	??0.010
??DI-3	??0.003	Oil-1	??0.20
??AS-2	??0.007	Oil-1	??0.20
??AS-2	??0.007	??AS-3	??0.035
Gelatin	??1.03	??AS-3	??0.035

The tenth layer: the yellow filter layer

Yellow colloidal silver	??0.053
Yellow colloidal silver	??0.053	??AS-1	??0.15
Oil-1	??0.15	??AS-1	??0.15
Oil-1	??0.15	Gelatin	??0.75

Eleventh floor: low speed blue sensitive layer

Iodine silver bromide latex emulsion g	??0.19
Iodine silver bromide latex emulsion g	??0.19	Iodine silver bromide latex emulsion e	??0.18
??SD-9	??1.14×10 ^-4	Iodine silver bromide latex emulsion e	??0.18
??SD-9	??1.14×10 ^-4	??SD-10	??1.62×10 ^-4
??SD-11	??4.39×10 ^-4	??SD-10	??1.62×10 ^-4
??SD-11	??4.39×10 ^-4	??Y-1	??0.90
??DI-3	??0.002	??Y-1	??0.90
??DI-3	??0.002	Oil-1	??0.29
??AS-2	??0.0014	Oil-1	??0.29
??AS-2	??0.0014	??X-1	??0.10
Gelatin	??1.49	??X-1	??0.10

Floor 12: high speed blue sensitive layer

Iodine silver bromide latex emulsion f	??0.71
Iodine silver bromide latex emulsion f	??0.71	Iodine silver bromide latex emulsion g	??0.20
??SD-9	??4.11×10 ^-5	Iodine silver bromide latex emulsion g	??0.20
??SD-9	??4.11×10 ^-5	??SD-10	??1.95×10 ^-5
??SD-11	??1.59×10 ^-4	??SD-10	??1.95×10 ^-5
??SD-11	??1.59×10 ^-4	??Y-1	??0.33
??DI-5	??0.12	??Y-1	??0.33
??DI-5	??0.12	Oil-1	??0.17
??AS-2	??0.010	Oil-1	??0.17
??AS-2	??0.010	??X-1	??0.098
Gelatin	??1.05	??X-1	??0.098

The 13 layer: first protective seam

Iodine silver bromide latex emulsion i	??0.20
Iodine silver bromide latex emulsion i	??0.20	??UV-1	??0.11
??UV-2	??0.055	??UV-1	??0.11
??UV-2	??0.055	??X-1	??0.078
Gelatin	??0.70	??X-1	??0.078

The 14 layer: second protective seam

????PM-1	????0.13
????PM-1	????0.13	????PM-2	????0.018
Wax-1	????0.021	????PM-2	????0.018
Wax-1	????0.021	Gelatin	????0.55

Below provide the characteristic of the iodine silver bromide latex emulsion that is used for sample 101, wherein average grain size is meant the cubical edge lengths with volume identical with crystal grain.

The average iodide diameter/thickness of emulsion average crystal grain chi

Very little (pm) content (mol%) ratio

a?????????1.00????????????3.2?????????7.0

b?????????0.70????????????3.3?????????6.5

c?????????0.30????????????1.9?????????5.5

d?????????0.45????????????4.0?????????6.0

E 0.27 2.0 cube

f?????????1.20????????????8.0?????????5.0

g?????????0.75????????????8.0?????????4.0

h?????????0.45????????????4.0?????????6.0

i?????????0.03????????????2.0?????????1.0

For aforementioned emulsion, except emulsion i, after aforementioned sensitizing dyestuff is added each emulsion and slaking emulsion, add the selenizing triphenyl phasphine, sodium thiosulfate, the common known method of gold chloride and potassium rhodanide and basis is carried out the relation of chemical sensitization between susceptibility and mist and is reached optimum.

Except above composition, also add coating additive SU-1, SU-2 and SU-3; Dispersing aid SU-4; Viscosity modifier V-1; Stabilizing agent ST-1; Two kinds of weight-average molecular weight are 10,000 and 1,100, and 000 polyvinyl pyrrolidone (AF-1, AF-2); Lime chloride; Inhibitor AF-3, AF-4, AF-5, Af-6 and AF-7; Rigidizer H-1; Antiseptic Ase-l.

Below provide the chemical constitution of the every kind of compound that is used for aforementioned sample.Y-1

M-1

M-2

C-1

C-2

C-3

CC-1

CM-1

CM-2

SD-1

SD-2

SD-3

SD-4

SD-6

SD-9

SD-10

SD-13

SD-14

SD-15

AS-1

AS-2

AS-3

AS-4

?????OIL-1????????????????????????????????UV-1

? OIL-2

H ₉C ₄OOC (CH ₂) ₉COOC ₄H ₉ V-1 N: degree of polymerization Ase-1 (potpourri)

A: B: C=50: 46: 4 (mol ratio) H-1

CH ₂=CHSO ₂-CH ₂CONHC ₂H ₄NHCOCH ₂-SO ₂CH=CH ₂ST-1

AF-1,2

AF-1 Mw_10,000AF-2 Mw_100,000n: degree of polymerization AF-3

AF-6

AF-7 X-1 X-2 SU-1

SU-2+C ₈F ₁₇SO ₂NH (CH ₂) ₃N (CH ₃) ₃Br-SU-3 SU-4

WAX-1 Mw=3,000PM-1 X: y: z=3: 3: 4PM-2 N: the degree of polymerization

The preparation of sample 102

Similar sample 101 preparation samples 102, just the 3rd layer iodine silver bromide latex emulsion h and the amount of e are changed into 0.39g/m respectively ²And 0.32g/m ²The 4th layer iodine silver bromide latex emulsion b and the amount of h are changed into 0.83g/m respectively ²And 0.36g/m ²The iodine silver bromide latex emulsion a of layer 5 and the amount of e are changed into 1.45g/m respectively ²And 0.076g/m ²The iodine silver bromide latex emulsion h of layer 7 and the amount of e are changed into 0.32g/m respectively ²And 0.11g/m ²The 8th layer iodine silver bromide latex emulsion b and the amount of h are changed into 0.66g/m respectively ²And 0.11g/m ²The 9th layer iodine silver bromide latex emulsion a and the amount of e are changed into 1.24g/m respectively ²And 0.076g/m ²The iodine silver bromide latex emulsion g of eleventh floor and the amount of e are changed into 0.23g/m respectively ²And 0.22g/m ²Change into 1.34g/m respectively with the iodine silver bromide latex emulsion f of Floor 12 and the amount of g ²And 0.25g/m ²The ISO speed of sample 102 is 1450.

The preparation of sample 103

According to the preparation of the emulsion EM-2 of the embodiment that is described in JP-A 2001-33903, prepare emulsion Em-1 and Em-2 with following characteristic, prerequisite is to optimize the pAg when being adjusted in crystal grain and forming and the joining day of corresponding solution.In addition, chemical sensitization and the spectral sensitization that these emulsions are stipulated.Be similar to sample 101 preparation samples 103, the iodine silver bromide latex emulsion a that just is used for layer 5 replaces with the emulsion Em-1 of equivalent silver amount, and the iodine silver bromide latex emulsion f that is used for the 9th layer iodine silver bromide latex emulsion a and is used for Floor 12 all replaces with the emulsion Em-2 of equivalent silver amount.The ISO speed of sample 103 is 630.

More than Zhi Bei emulsion Em-1 be a kind of be 2.8 μ m by average crystal grain diameter, crystal grain diameter distribute (that is the grain size distribution coefficient of variation) be 18% and the iodine silver bromide latex emulsion formed of the sexangle sheet crystal grain of mean aspect ratio 16.Electron microscope observation shows that total crystal grain projected area of 90% is occupied by the silver halide grain that has 5 bunk lines in the marginal portion at least and total crystal grain projected area of 70% is occupied by the silver halide grain that has 20 bunk lines in the marginal portion at least.In addition, emulsion Em-2 is to be 3.5 μ m by average crystal grain diameter, and it is the iodine silver bromide latex emulsion that sexangle sheet crystal grain that 20 flaky crystalline grain occupies is formed by length breadth ratio that crystal grain diameter is distributed as 20% and 50% total crystal grain projected area.Electron microscope observation shows that total crystal grain projected area of 90% is occupied by the silver halide grain that has 5 bunk lines in the marginal portion at least and total crystal grain projected area of 70% is occupied by the silver halide grain that has 20 bunk lines in the marginal portion at least.

The preparation of sample 104

Emulsion Em-3 (having average crystal grain thickness 0.055 μ m and average crystal grain diameter 0.42 μ m) and Em-4 (having average crystal grain thickness 0.057 μ m and average crystal grain diameter 0.44 μ m) make according to the preparation of the emulsion EM-2 of the embodiment that is described in JP-A 2001-33903.In addition, chemical sensitization and the spectral sensitization that these emulsions are stipulated.

Be similar to sample 101 preparation samples 104, the iodine silver bromide latex emulsion a that just is used for layer 5 replaces with the emulsion Em-3 of equivalent silver amount, and the iodine silver bromide latex emulsion f that is used for the 9th layer iodine silver bromide latex emulsion a and is used for Floor 12 replaces with the emulsion Em-4 of equivalent silver amount respectively.The ISO speed of sample 103 turns out to be 430.

The preparation of sample 105

Sample 105 is similar to sample 104 preparations, and the amount that just is used for the emulsion Em-3 of layer 5 is changed into 1.24g/m ², the amount that is used for the 9th layer emulsion Em-4 is changed into 1.34g/m ², the amount that is used for the C-3 of layer 5 is changed into 0.34g/m ², the amount that is used for the 9th layer M-2 is changed into 0.20g/m ²And the amount that is used for the Y-1 of Floor 12 is changed into 0.50g/m ². the ISO speed of sample 103 turns out to be 775.

The assessment of sample

According to the aging respectively sample 101-105 that will so make of following step and the size of assessing dye cloud and minimum and maximal density (also being called Dmin and Dmax simply) and the susceptibility before or after carrying out accelerated aging test (also being called S simply).

Technology 101

Prepare two-part corresponding sample.Wherein a part is assessed according to following steps.Another part aging 2 weeks and assess as follows subsequently under 55 ℃ and 65%RH.

To wear out and not aged sample under 200lux, exposed 1/100 second by optical wedge according to defined method among the ANSI PH2.27.After exposure, sample is handled according to color negative film standard technology C-41 (Eastman Kodak Co.), and wherein colour development was carried out under 35 ℃ 195 seconds.Use transmission-type opacimeter (being produced by X-rite Co.) with red in the sample of so handling, green and blue light carries out densitometric analysis, obtains the family curve of being made up of horizontal ordinate-exposure (LogE) and ordinate-optics (D).According to the family curve of each sample that so obtains, determine minimum and high density.Difference when least density deducts base density and the difference when high density deducts base density are defined as minimum density (Dmin) and maximal density (Dmax) respectively.Susceptibility is defined as and obtains least density (that is inverse of the required exposure of density Dmin+0.1), that adds 0.1.Susceptibility is expressed as relative value, and wherein the susceptibility of unaged sample is 100.

The part that each unaged sample is had the density of Dmin+0.1 is carried out the mean diameter that 500 dye cloud were observed and determined to dye cloud with microscope.

Base density is determined as follows.Sample is just only removed color developer according to handling with the same way as of aforementioned C-41 technology from colour development solution.With the gained yellow, (Y, N C) are defined as base density for magenta and cyan density.

Technology 102

Technology 102 is similar to aforementioned technology 101 carries out, and just the treatment conditions in the colour development are changed into 50 ℃ and 60 seconds by 38 ℃ and 195 seconds.Assessment is similar to technology 101 and carries out.

Technology 103

Technology 103 is similar to aforementioned technology 101 carries out, and just the treatment conditions in the colour development are changed into 45 ℃ and 120 seconds by 38 ℃ and 195 seconds.Assessment is similar to technology 101 and carries out.

In the aforementioned assessment result of sample 101-105, the characteristic value of green sensitive layer (magenta dye image) is shown in table 1.Table 1

Imaging number	The photograph sample number	Technology number	Magenta dye cloud diameter (μ m)	Unaged sample			Aged samples			Note
				Unaged sample			Aged samples				????Dmin	???Dmax	????S	???Dmin	???Dmax	????S
				????1-1	????101	????101	??????2.7	????0.05	???1.83		????Dmin	???Dmax	????S	???Dmin	???Dmax	????S	???100	???0.32	???1.74	???92	Comparative Examples
????1-2	????103	????101	??????2.8	????1-1	????101	????101	??????2.7	????0.05	???1.83	????0.19	???1.79	???100	???0.40	???1.60	???89	Comparative Examples	???100	???0.32	???1.74	???92	Comparative Examples
????1-2	????103	????101	??????2.8	????1-3	????104	????101	??????2.2	????0.17	???1.81	????0.19	???1.79	???100	???0.40	???1.60	???89	Comparative Examples	???100	???0.35	???1.61	???91	Comparative Examples
????1-4	????105	????101	??????2.7	????1-3	????104	????101	??????2.2	????0.17	???1.81	????0.20	???1.84	???100	???0.37	???1.68	???93	Comparative Examples	???100	???0.35	???1.61	???91	Comparative Examples
????1-4	????105	????101	??????2.7	????1-5	????101	????103	??????2.8	????0.15	???1.82	????0.20	???1.84	???100	???0.37	???1.68	???93	Comparative Examples	???100	???0.27	???1.73	???93	Comparative Examples
????1-6	????102	????101	??????3.1	????1-5	????101	????103	??????2.8	????0.15	???1.82	????0.22	???1.81	???100	???0.29	???1.75	???91	Comparative Examples	???100	???0.27	???1.73	???93	Comparative Examples
????1-6	????102	????101	??????3.1	????1-7	????102	????102	??????3.5	????0.00	???1.90	????0.22	???1.81	???100	???0.29	???1.75	???91	Comparative Examples	???100	???0.07	???1.91	???100	The present invention
????1-8	????103	????102	??????3.9	????1-7	????102	????102	??????3.5	????0.00	???1.90	????0.01	???1.95	???100	???0.10	???1.97	???101	The present invention	???100	???0.07	???1.91	???100	The present invention
????1-8	????103	????102	??????3.9	????1-9	????104	????102	??????3.8	????0.00	???1.89	????0.01	???1.95	???100	???0.10	???1.97	???101	The present invention	???100	???0.12	???1.85	???99	The present invention
????1-10	????105	????102	??????3.2	????1-9	????104	????102	??????3.8	????0.00	???1.89	????0.01	???1.92	???100	???0.09	???1.91	???99	The present invention	???100	???0.12	???1.85	???99	The present invention
????1-10	????105	????102	??????3.2	????1-11	????102	????103	??????3.2	????0.01	???1.81	????0.01	???1.92	???100	???0.09	???1.91	???99	The present invention	???100	???0.19	???1.78	???97	The present invention

Can clearly find out from table 1, color imaging method of the present invention, that is, the combination of photographic material of the present invention and technology has obtained the susceptibility that increases, excellent rapid processing performance and improved storage stability.Although do not provide in table 1, similar results also obtains when yellow and product color image.

In addition, be applied to the sample of above-mentioned processing, can confirm that silver and carrier are suitably reclaimed by the method for utilizing again that will be described in JP-A 11-72891.

Embodiment 2

The preparation of color silver halide photographic-material

The preparation of sample 201

Thick at 96 μ m, on the bottom polyphenyl dioctyl phthalate glycol ester film carrier, form have show down composition with lower floor, obtain multi layer colour photographic material sample 201.ISO speed according to the definite sample 201 of the method for ANSI PH2.27 is 250.The addition of every kind of compound is expressed as g/m ²Unless, refer else.The scale that the amount of silver halide or collargol changes into silver amount and sensitizing dyestuff (being expressed as " SD ") be shown mol/Ag mol. be used for the iodine silver bromide latex emulsion of sample 201 and additive kind be similar to early provide be used for those of sample 101.Behenic acid silver is according to JP-A2002-55410, and 0096-0097 controls, and to wherein further adding ST-2.Gained behenic acid silver has 28% monodispersity (that is grain size distribution coefficient) ground floor: anti-halation layer

The black collargol	????0.16
The black collargol	????0.16	????UV-1	????0.30
????CM-1	????0.12	????UV-1	????0.30
????CM-1	????0.12	Oil-1	????0.24
????AP-1	????0.65	Oil-1	????0.24
????AP-1	????0.65	Gelatin	????1.33

The second layer: middle layer

Iodine silver bromide latex emulsion i	??0.06
Iodine silver bromide latex emulsion i	??0.06	??AS-1	??0.12
Oil-1	??0.15	??AS-1	??0.12
Oil-1	??0.15	??DP-1	??0.50
Gelatin	??0.67	??DP-1	??0.50

The 3rd layer: the low speed red-sensitive layer

Iodine silver bromide latex emulsion h	??0.39
Iodine silver bromide latex emulsion h	??0.39	Iodine silver bromide latex emulsion e	??0.32
??SD-1	??2.22×10 ^-4	Iodine silver bromide latex emulsion e	??0.32
??SD-1	??2.22×10 ^-4	??SD-2	??3.72×10 ^-5
??SD-3	??1.56×10 ^-4	??SD-2	??3.72×10 ^-5
??SD-3	??1.56×10 ^-4	??SD-4	??3.41×10 ^-4
??C-1	??0.77	??SD-4	??3.41×10 ^-4
??C-1	??0.77	??CC-1	??0.006
Oil-2	??0.47	??CC-1	??0.006
Oil-2	??0.47	??AS-2	??0.002
Hot solvent TS-1	??0.23	??AS-2	??0.002
Hot solvent TS-1	??0.23	Behenic acid silver	??1.82
Gelatin	??1.82	Behenic acid silver	??1.82

The 4th layer: the middling speed red-sensitive layer

Iodine silver bromide latex emulsion b	??0.83
Iodine silver bromide latex emulsion b	??0.83	Iodine silver bromide latex emulsion h	??0.36
??SD-1	??3.46×10 ^-4	Iodine silver bromide latex emulsion h	??0.36
??SD-1	??3.46×10 ^-4	??SD-2	??2.44×10 ^-5
??SD-4	??3.69×10 ^-4	??SD-2	??2.44×10 ^-5
??SD-4	??3.69×10 ^-4	??C-1	??0.42
Oil-2	??0.27	??C-1	??0.42
Oil-2	??0.27	??AS-2	??0.003
Hot solvent TS-1	??0.28	??AS-2	??0.003
Hot solvent TS-1	??0.28	Behenic acid silver	??0.62
Oxygenant OH-1	??0.05	Behenic acid silver	??0.62
Oxygenant OH-1	??0.05	Gelatin	??1.45

Layer 5: high speed red-sensitive layer

Iodine silver bromide latex emulsion a	??1.45
Iodine silver bromide latex emulsion a	??1.45	Iodine silver bromide latex emulsion e	??0.076
??SD-2	??1.35×10 ^-5	Iodine silver bromide latex emulsion e	??0.076
??SD-2	??1.35×10 ^-5	??SD-12	??2.43×10 ^-4
??SD-4	??6.45×10 ^-5	??SD-12	??2.43×10 ^-4
??SD-4	??6.45×10 ^-5	??C-2	??0.10
??C-3	??0.17	??C-2	??0.10
??C-3	??0.17	Oil-2	??0.17
??AS-2	??0.004	Oil-2	??0.17
??AS-2	??0.004	Hot solvent TS-1	??0.33
Behenic acid silver	??0.82	Hot solvent TS-1	??0.33
Behenic acid silver	??0.82	Oxygenant OH-1	??0.06
Gelatin	??1.21	Oxygenant OH-1	??0.06

Layer 6: middle layer

????Y-1	????0.08
????Y-1	????0.08	????AS-1	????0.11
Oil-1	????0.17	????AS-1	????0.11
Oil-1	????0.17	????X-2	????0.005
????DP-1	????0.55	????X-2	????0.005
????DP-1	????0.55	Gelatin	????0.87

Layer 7: low speed green sensitive layer

Iodine silver bromide latex emulsion h	??0.32
Iodine silver bromide latex emulsion h	??0.32	Iodine silver bromide latex emulsion e	??0.11
??SD-14	??3.6×10 ^-5	Iodine silver bromide latex emulsion e	??0.11
??SD-14	??3.6×10 ^-5	??SD-15	??4.2×10 ^-4
??M-1	??0.375	??SD-15	??4.2×10 ^-4
??M-1	??0.375	Oil-1	??0.41
??AS-2	??0.02	Oil-1	??0.41
??AS-2	??0.02	??AS-3	??0.11
Hot solvent TS-1	??0.21	??AS-3	??0.11
Hot solvent TS-1	??0.21	Behenic acid silver	??0.43
Oxygenant OH-1	??0.03	Behenic acid silver	??0.43
Oxygenant OH-1	??0.03	Gelatin	??1.21

The 8th layer: the middling speed green sensitive layer

Iodine silver bromide latex emulsion b	??0.66
Iodine silver bromide latex emulsion b	??0.66	Iodine silver bromide latex emulsion h	??0.11
??SD-13	??3.7×10 ^-4	Iodine silver bromide latex emulsion h	??0.11
??SD-13	??3.7×10 ^-4	??SD-6	??3.44×10 ^-4
??SD-8	??1.05×10 ^-4	??SD-6	??3.44×10 ^-4
??SD-8	??1.05×10 ^-4	??M-1	??0.18
Oil-1	??0.23	??M-1	??0.18
Oil-1	??0.23	??AS-3	??0.046
??AS-4	??0.006	??AS-3	??0.046
??AS-4	??0.006	Hot solvent TS-1	??0.23
Behenic acid silver	??0.39	Hot solvent TS-1	??0.23
Behenic acid silver	??0.39	Oxygenant OH-1	??0.04
Gelatin	??1.01	Oxygenant OH-1	??0.04

The 9th layer: the high speed green sensitive layer

Iodine silver bromide latex emulsion a	??1.24
Iodine silver bromide latex emulsion a	??1.24	Iodine silver bromide latex emulsion e	??0.076
??SD-13	??8.0×10 ^-5	Iodine silver bromide latex emulsion e	??0.076
??SD-13	??8.0×10 ^-5	??SD-6	??3.42×10 ^-4
??SD-8	??1.04×10 ^-4	??SD-6	??3.42×10 ^-4
??SD-8	??1.04×10 ^-4	??M-1	??0.038
??M-2	??0.078	??M-1	??0.038
??M-2	??0.078	Oil-1	??0.20
??AS-2	??0.007	Oil-1	??0.20
??AS-2	??0.007	??AS-3	??0.035
Hot solvent TS-1	??0.38	??AS-3	??0.035
Hot solvent TS-1	??0.38	Behenic acid silver	??0.41
Oxygenant OH-1	??0.03	Behenic acid silver	??0.41
Oxygenant OH-1	??0.03	Gelatin	??1.03

The tenth layer: the yellow filter layer

Yellow colloidal silver	??0.053
Yellow colloidal silver	??0.053	??AS-1	??0.15
Oil-1	??0.18	??AS-1	??0.15
Oil-1	??0.18	??DP-1	??0.42
Gelatin	??0.75	??DP-1	??0.42

Eleventh floor: low speed blue sensitive layer

Iodine silver bromide latex emulsion g	??0.23
Iodine silver bromide latex emulsion g	??0.23	Iodine silver bromide latex emulsion e	??0.22
??SD-9	??1.14×10 ^-4	Iodine silver bromide latex emulsion e	??0.22
??SD-9	??1.14×10 ^-4	??SD-10	??1.62×10 ^-4
??SD-11	??4.39×10 ^-4	??SD-10	??1.62×10 ^-4
??SD-11	??4.39×10 ^-4	??Y-1	??0.90
Oil-1	??0.29	??Y-1	??0.90
Oil-1	??0.29	??AS-2	??0.014
??X-1	??0.10	??AS-2	??0.014
??X-1	??0.10	Hot solvent TS-1	??0.28
Behenic acid silver	??0.29	Hot solvent TS-1	??0.28
Behenic acid silver	??0.29	Oxygenant OH-1	??0.02
Gelatin	??1.49	Oxygenant OH-1	??0.02

Floor 12: high speed blue sensitive layer

Iodine silver bromide latex emulsion f	??1.34
Iodine silver bromide latex emulsion f	??1.34	Iodine silver bromide latex emulsion g	??0.25
??SD-9	??4.11×10 ^-5	Iodine silver bromide latex emulsion g	??0.25
??SD-9	??4.11×10 ^-5	??SD-10	??1.95×10 ^-5
??SD-11	??1.59×10 ^-4	??SD-10	??1.95×10 ^-5
??SD-11	??1.59×10 ^-4	??Y-1	??0.33
Oil-1	??0.17	??Y-1	??0.33
Oil-1	??0.17	??AS-2	??0.010
Hot solvent TS-1	??0.41	??AS-2	??0.010
Hot solvent TS-1	??0.41	Behenic acid silver	??0.33
Oxygenant OH-1	??0.04	Behenic acid silver	??0.33
Oxygenant OH-1	??0.04	Gelatin	??1.05

The 13 layer: first protective seam

The 14 layer: second protective seam

The preparation of sample 202

Be similar to sample 201 preparation samples 202, just the the the three, the four, the five, the seven, the the eight, the nine, the 11 and the gelatin amount of Floor 12 change into separately 0.7 times.

Preparation sample 203 to 207

Sample 203-207 is similar to sample 202 preparation, just is used for the CDP-1 that second and the tenth layer DP-1 replaces with equimolar amounts respectively, CDP-2, CDP-3, CDP-4, and CDP-5.

The preparation of sample 208

Sample 208 is similar to sample 201 preparations, just with 0.21g/m ²4-methylphthalic acid and 0.43g/m ²Phthalazone add the five, the nine and Floor 12 in each the layer.

The preparation of sample 209

Sample 209 is similar to sample 201 preparation, just ET-1 with the amount of the 0.1mol% silver of corresponding layer add the five, the nine and Floor 12 in each layer.

The preparation of sample 210

Sample 210 is similar to sample 201 preparation, just HO-1 with the amount of the 0.2mol% silver of corresponding layer add the five, the nine and Floor 12 in each layer.

The preparation of sample 211

Sample 211 is similar to sample 201 preparations, and just preparation technology's change makes that monodispersity is 8%.

The preparation of sample 212

Sample 212 is similar to sample 201, just is used for the three, the four and the C-1 of layer 5, and C-2 and C-3 replace with the C-6 that is described in JP-B 6-64319 of equimolar amounts respectively; Be used for the MM-2 that is described in aforementioned publication that the the seven, the eight and the 9th layer M-1 and M-2 replace with equimolar amounts; Be used for the 11 and the Y-1 of Floor 12 replace with the Y-3 that is described in aforementioned publication of equimolar amounts, and every kind of aforementioned substances adds to be similar to the method that is described in aforementioned publication.

The preparation of sample 213

Sample 213 is similar to sample 201 preparation, just CDS-1 with the amount of the 10mol% colour coupler of corresponding layer add the five, the nine and Floor 12 in each layer.

Except being described in those of embodiment 1, below provide the compound that is used for aforementioned sample.AP-1

CDP-5????????????????????????????????????????TS-1 ??

ST-2?????????????????????????????????????????OH-1 ? ??????????????????????

The assessment of sample

The sample 201-213 that so makes according to following step process and assess the dye cloud size and minimum and maximal density (Dmin and Dmax) and the susceptibility (5) before or after carrying out accelerated aging test respectively.

Prepare two-part corresponding sample 201-213.Wherein a part is assessed according to following steps.Another part aging two weeks and assess as follows subsequently under 55 ℃ and 65%RH.

To wear out and not aged sample under 200lux, exposed 1/100 second by optical wedge according to defined method among the ANSI PH2.27.After exposure, sample heated 30 seconds down at 120 ℃ respectively.After heating, sample is bleached photographic fixing and stabilization respectively according to color negative film standard technology C-41 (Eastman KodakCo.).This technology refers to technology 201.Use transmission-type opacimeter (being produced by X-rite Co.) with red in the sample of so handling, green and blue light carries out densitometric analysis, obtains the family curve of being made up of horizontal ordinate-exposure (LogE) and ordinate-optics (D).According to the family curve of each sample that so obtains, determine minimum and high density.Difference when least density deducts base density and the difference when high density deducts base density are defined as least density (Dmin) and maximal density (Dmax) respectively.Susceptibility is defined as and obtains least density (that is inverse of the required exposure of density Dmin+0.1), that adds 0.1.Susceptibility is expressed as relative value, and wherein the susceptibility of unaged sample is 100.

The part that will have the density of Dmin+0.1 is carried out the mean diameter that 500 dye cloud were observed and determined to dye cloud with microscope.

In the aforementioned assessment result of sample, the characteristic value of green sensitive layer (magenta dye image) is shown in table 2.

Table 2

Imaging number	The photograph sample number	Technology number	Magenta dye cloud diameter (μ m)	Unaged sample			Aged samples			Note
				Unaged sample			Aged samples				???Dmin	????Dmax	?????S	????Dmin	???Dmax	???S
				????2-1	???201	????201	??????0.8	???0.19	????1.73		???Dmin	????Dmax	?????S	????Dmin	???Dmax	???S	????100	????0.53	???1.55	???89	Comparative Examples
????2-2	???202	????201	??????3.3	????2-1	???201	????201	??????0.8	???0.19	????1.73	???0.02	????1.92	????100	????0.19	???1.90	???97	The present invention	????100	????0.53	???1.55	???89	Comparative Examples
????2-2	???202	????201	??????3.3	????2-3	???203	????201	??????4.3	???0.00	????1.93	???0.02	????1.92	????100	????0.19	???1.90	???97	The present invention	????100	????0.10	???1.92	???100	The present invention
????2-4	???204	????201	??????3.9	????2-3	???203	????201	??????4.3	???0.00	????1.93	???0.01	????1.90	????100	????0.11	???1.91	???99	The present invention	????100	????0.10	???1.92	???100	The present invention
????2-4	???204	????201	??????3.9	????2-5	???205	????201	??????4.2	???0.02	????1.91	???0.01	????1.90	????100	????0.11	???1.91	???99	The present invention	????100	????0.12	???1.89	???98	The present invention
????2-6	???206	????201	??????3.4	????2-5	???205	????201	??????4.2	???0.02	????1.91	???0.09	????1.84	????100	????0.20	???1.80	???97	The present invention	????100	????0.12	???1.89	???98	The present invention
????2-6	???206	????201	??????3.4	????2-7	???207	????201	??????3.3	???0.02	????1.90	???0.09	????1.84	????100	????0.20	???1.80	???97	The present invention	????100	????0.09	???1.91	???99	The present invention
????2-8	???208	????201	??????3.5	????2-7	???207	????201	??????3.3	???0.02	????1.90	???0.07	????1.88	????100	????0.21	???1.88	???97	The present invention	????100	????0.09	???1.91	???99	The present invention
????2-8	???208	????201	??????3.5	????2-9	???209	????201	??????4.1	???0.08	????1.85	???0.07	????1.88	????100	????0.21	???1.88	???97	The present invention	????100	????0.18	???1.80	???95	The present invention
????2-10	???210	????201	??????3.8	????2-9	???209	????201	??????4.1	???0.08	????1.85	???0.05	????1.87	????100	????0.22	???1.85	???96	The present invention	????100	????0.18	???1.80	???95	The present invention
????2-10	???210	????201	??????3.8	????2-11	???211	????201	??????4.3	???0.09	????1.88	???0.05	????1.87	????100	????0.22	???1.85	???96	The present invention	????100	????0.15	???1.90	???97	The present invention
????2-12	???212	????201	??????3.2	????2-11	???211	????201	??????4.3	???0.09	????1.88	???0.02	????1.85	????100	????0.14	???1.83	???99	The present invention	????100	????0.15	???1.90	???97	The present invention
????2-12	???212	????201	??????3.2	????2-13	???213	????201	??????6.7	???0.04	????1.89	???0.02	????1.85	????100	????0.14	???1.83	???99	The present invention	????100	????0.08	???1.88	???99	The present invention

Can find out clearly that from table 2 in comprising the photothermographic material of color developer, the sample that comprises composition of the present invention causes having the susceptibility of increase, the excellent rapid processing performance and the color imaging method of improved storage stability.Although do not provide in table 1, similar results obtains when yellow and magenta color image.

In addition, be applied to the sample of above-mentioned processing, can confirm that silver and carrier are suitably reclaimed owing to will be described in the method for utilizing again of JP-A 11-72891.

Embodiment 3

The photograph sample that to make in embodiment 1 and 2 transforms respectively and is packaged in the box according to 135 size film standards.Use these film samples and the single lens reflex camera of being furnished with the camera lens (F4, the product of Nikon Corp.) of 35mm focal length and F:2, to comprising the personage, flower, green plants, 5 scenes of mountain range and blue sky are taken a picture at a distance, are 800 with the ISO speed setting wherein.Then, the film sample of exposure is carried out colour development according to the method that is described in embodiment 1 and 2, further do not bleach, photographic fixing and stabilization process are wherein left the development sample of developed silver and silver halide.

Film by development like this, use the monochromatic CCD camera (KX4 of 2048 * 2048 pixels, derive from Eastman Kodak Co.) obtain R, G separates negative-appearing image with B, wherein red sub is from light filter (gelatin light filter W26, derive from Eastman Kodak Co.), green sub is arranged between light source and the film from light filter (W99) or the blue light filter (W98) that separates.The rgb image data that uses LED printer (deriving from KonicaCorp.) so to obtain outputs to the A4-size, and (210mm * 297mm) and 2L-size are (on the QAA7 type Konica chromatics paper of 127mm * 178mm) to obtain chromatograp.

At the sharpness and the grainy appearance of image, the vividness of green plants and the Apparent Depth on mountain range, 10 people carry out the sense organ test to the chromatograp that so obtains.The result confirms that the chromatograp that the sample that use is obtained by technology of the present invention is made never is worse than the image that obtains in routine photograph system.

Embodiment 4

The sample that will be used for embodiment 3 develops, and further bleaches photographic fixing and stabilization process subsequently according to the C41 standard technology.The sample of so handling is similar to embodiment 3 to be assessed.The result confirms that the gained printed matter never is worse than the image that obtains in routine photograph system.

Embodiment 5

To be used for the sample development of embodiment 3 and use the CCD camera to read.Then, the development sample is further bleached photographic fixing and stabilization process according to the C41 standard technology.Then, be similar to embodiment 3, the sample of handling read with the CCD camera and by gained R, G separates negative-appearing image with B, obtain being proved the chromatograp that never is worse than the image that in routine photograph system, obtains.

Embodiment 6

Be similar to 3 pairs of samples of embodiment and handle and assess, prerequisite is that image correction process is carried out based on the infrared light of transmission by the photographic material sample according to the method that is described in JP-A 6-28468 if the sample of handling uses the CCD camera to read.The result confirms, the image that it never is worse than or is better than obtaining in routine photograph system.Carry out timing at use infrared external reflection light and also obtain similar results.

Embodiment 7

Be similar to embodiment 1 and handle and assess, only be to use the treatment element of the embodiment 1 that is described in JP-A2002-55418 to carry out colour development.Be similar to embodiment 1, confirm the invention provides the color imaging method of a kind of susceptibility that obtains to increase and the storage stability of excellence.

Claims

1. method that forms coloured image comprises:

To comprise the color silver halide photographic-material imaging exposure of carrier, described carrier have thereon at least one comprise silver halide grain and form the silver halide photosensitive layer of colour coupler of dyestuff and the insensitive layer of at least one light and

The photographic material of exposure is developed under 43-180 ℃ of temperature with the formation coloured image,

Wherein, add 0.1 transmission density if the photographic material exposure makes the photosensitive layer that develops have least density, the photosensitive layer of this development comprises the dye cloud that mean diameter is 3.0-20.0 μ m.

2. the process of claim 1 wherein that development temperature is 50 ℃-160 ℃.

3. the process of claim 1 wherein photosensitive layer be selected from the blue sensitive layer that comprises blue sensitive silver halide crystal grain and can form the colour coupler of weld, comprise the green sensitive silver halide grain and can form magenta dye colour coupler green sensitive layer and comprise the red sensitive silver halide grain and can form a kind of in the red-sensitive layer of colour coupler of cyan dye.

4. the process of claim 1 wherein that photographic material has 800 the ISO speed of being not less than.

5. the process of claim 1 wherein that silver halide grain forms by having the flaky crystalline grain that is not less than 8 mean aspect ratio.

6. the method for claim 5, wherein the average thickness of flaky crystalline grain is 0.01-0.07 μ m.

7. the process of claim 1 wherein at least a color developer or its precursor of comprising in the insensitive layer of photosensitive layer and light.

8. the method for claim 7, wherein said precursor is a kind of compound that can discharge p-phenylenediamine (PPD) type color developer.

9. the process of claim 1 wherein at least a picture tone modifier that comprises in the insensitive layer of photosensitive layer and light.

10. the process of claim 1 wherein at least a electron transfer agent that comprises in the insensitive layer of photosensitive layer and light.

11. the process of claim 1 wherein at least a hydrazine derivate that comprises in the insensitive layer of photosensitive layer and light.

12. the process of claim 1 wherein that photosensitive layer comprises the organic silver salts crystal grain that the crystallite dimension coefficient of variation is 0.1-25%.

13. the process of claim 1 wherein that the colour coupler that can form dyestuff is a Fischer type colour coupler.

14. the process of claim 1 wherein that photosensitive layer comprises when with the reaction of the oxidation product of color developer can form the compound of colourless compound basically.

15. a method that forms coloured image comprises step:

(a) the color silver halide photographic-material imaging that will comprise carrier exposes, and described carrier has at least one silver halide photosensitive layer and insensitive layer of at least one light that comprises silver halide grain and form the colour coupler of dyestuff thereon,

(b) photographic material with exposure develops under 43-180 ℃ of temperature with the formation coloured image,

(c) information with formed coloured image changes into digital image information by imageing sensor,

16. the method for claim 15 wherein in step (c), adopts the light by the photographic material reflection.

17. the method for claim 15 wherein in step (c), adopts infrared light.

18. the method for claim 15 is wherein carried out step (c) and is not removed silver halide or the insensitive silver compound of light that is included in the photographic material.

19. the method for claim 15, wherein in step (c) before, this method further comprises step:

The photographic material that (b ') will carry out colour development carries out at least a bleaching that is selected from, and the processing of photographic fixing and stabilization obtains coloured image.

20. a method that forms coloured image comprises step:

Wherein, if the photographic material exposure makes the photosensitive layer that develops have least density and adds 0.1 transmission density, the photosensitive layer of this development comprises the dye cloud that mean diameter is 3.0-20.0 μ m, and carries out step (c) and do not remove silver halide or the insensitive silver compound of light that is included in the photographic material;

And wherein, photographic material has 800 the ISO speed of being not less than, silver halide grain is formed by having the flaky crystalline grain that is not less than 8 mean aspect ratio, and the insensitive layer of light comprises color developer or its precursor, and the photosensitive layer organic silver salts crystal grain that to comprise a kind of crystallite dimension coefficient of variation be 0.1-25%.